U.S. patent number 5,830,625 [Application Number 08/679,317] was granted by the patent office on 1998-11-03 for silver halide color photographic material and processing method thereof.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Shigeo Hirano.
United States Patent |
5,830,625 |
Hirano |
November 3, 1998 |
Silver halide color photographic material and processing method
thereof
Abstract
A silver halide color photographic material is disclosed,
comprising a support having thereon at least two light-sensitive
silver halide emulsion layers, the lowermost light-sensitive silver
halide emulsion layer and/or a light-insensitive layer adjacent
thereto containing a compound represented by formula (D): ##STR1##
wherein R.sup.1 and R.sup.2 each represents an alkyl group, an aryl
group or a heterocyclic group, R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 each represents a hydrogen atom, a halogen atom or a
substituent connecting to the benzene ring through a carbon atom,
an oxygen atom, a nitrogen atom or a sulfur atom, R.sup.1 and
R.sup.2, R.sup.1 and R.sup.3, R.sup.3 and R.sup.4, R.sup.2 and
R.sup.5 or R.sup.5 and R.sup.6 may be combined to form a ring,
R.sup.7 represents a hydrogen atom or forms=(T).sub.m S together
with -(T).sub.m S, T represents a timing group, m represents an
integer of 0 to 3 and S represents a protective group eliminated at
the development. Also disclosed is a method for processing the
photographic material.
Inventors: |
Hirano; Shigeo (Kanagawa,
JP) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JP)
|
Family
ID: |
15527058 |
Appl.
No.: |
08/679,317 |
Filed: |
July 12, 1996 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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481076 |
Jun 7, 1995 |
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Foreign Application Priority Data
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|
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Jun 10, 1994 [JP] |
|
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6-151821 |
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Current U.S.
Class: |
430/435; 430/405;
430/434; 430/486; 430/505; 430/959; 430/502; 430/484; 430/467;
430/464 |
Current CPC
Class: |
G03C
7/39224 (20130101); G03C 7/4136 (20130101); G03C
7/3022 (20130101); G03C 2200/52 (20130101); G03C
2001/03558 (20130101); G03C 2200/21 (20130101); G03C
2200/53 (20130101); Y10S 430/16 (20130101); G03C
7/3003 (20130101) |
Current International
Class: |
G03C
7/392 (20060101); G03C 7/30 (20060101); G03C
7/413 (20060101); G03C 005/18 (); G03C
005/26 () |
Field of
Search: |
;430/464,467,484,405,505,959,502,567,546,443,486,434,435 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Letscher; Geraldine
Attorney, Agent or Firm: Sughrue, Mion, Zinn, Macpeak &
Seas, PLLC
Parent Case Text
This is a Divisional of application Ser. No. 08/481,076 filed Jun.
7, 1995, now abandoned.
Claims
What is claimed is:
1. A method for processing a silver halide color photographic
material comprising a support having thereon in the following
order: a red-sensitive silver halide emulsion layer (R layer), a
green-sensitive silver halide emulsion layer (G layer) and a
blue-sensitive silver halide emulsion layer (B layer), the red
sensitive layer being lowermost with respect to the support, a
silver halide emulsion having an iodide content of from 3 to 15
mole %, the lowermost light-sensitive silver halide emulsion layer
with respect to the support and/or a light-insensitive layer
adjacent thereto containing fine particles of a compound
represented by formula (D), with a color developer containing a
paraphenylenediamine-based color forming developing agent: ##STR8##
wherein R.sup.1 and R.sup.2 each represents an alkyl group, an aryl
group or a heterocyclic group, R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 each represents a hydrogen atom, a halogen atom or a
substituent connecting to the benzene ring through a carbon atom,
an oxygen atom, a nitrogen atom or a sulfur atom, R.sup.1 and
R.sup.2, R.sup.1 and R.sup.3, R.sup.3 and R.sup.4, R.sup.2 and
R.sup.5 or R.sup.5 and R.sup.6 may be combined to form a ring,
R.sup.7 represents a hydrogen atom or forms=(T).sub.m S together
with -(T).sub.m S, T represents a timing group, m represents an
integer of 0 to 3 and S represents a protective
group eliminated at the development, wherein the processing time of
color development is from 30 to 90 seconds.
2. A method for processing the photographic material as claimed in
claim 1, wherein said compound of formula (D) is one represented by
formula (E) ##STR9## wherein R.sup.1, R.sup.2, R.sup.4, R.sup.7, T,
S and m each has the same meaning as in.
3. A method for processing a silver halide color photographic
material comprising a support having thereon in the following
order: a red-sensitive silver halide emulsion layer (R layer), a
green-sensitive silver halide emulsion layer (G layer) and a
blue-sensitive silver halide emulsion layer (B layer), the
red-sensitive layer being lowermost with respect to the support, a
silver halide emulsion having an iodide content of from 3 to 15
mole %, the lowermost light-sensitive silver halide emulsion layer
to the support and/or a light-insensitive layer adjacent thereto
containing fine particles of a compound represented by formula (E),
with a color developer containing a paraphenylenediamine-based
color forming developing agent: ##STR10## R.sup.1 and R.sup.2 each
independently is an unsubstituted alkyl or hydroxyalkyl group,
R.sup.1 and R.sup.2 are combined to form a 5-membered ring, or
R.sup.1 is combined with the benzene ring to form a 5- or
6-membered ring;
R.sup.4 is an alkyl ring group or an alkoxy group; and
R.sup.7 is H,
wherein T represents a timing group, m represents an integer of 0
to 3 and S represents a protective group eliminated at development,
and
wherein the processing time of color development is from 30 to 90
seconds.
4. A method for processing the photographic material as claimed in
claim 1, wherein said compound of formula (D) is used in an amount
of from 2.times.10.sup.-2 to 10 mmol/m.sup.2.
5. A method for processing the photographic material as claimed in
claim 1, wherein said compound of formula (D) is used in an amount
of from 1.times.10.sup.-1 to 6 mmol/m.sup.2.
6. A method for processing the photographic material as claimed in
claim 1, wherein said compound of formula (D) has an average
particle size of 0.01 .mu.m to 10 .mu.m in a dispersion.
7. A method for processing the photographic material as claimed in
claim 1, wherein said compound of formula (D) has an average
particle size of 0.01 .mu.m to 5 .mu.m in a dispersion.
8. A method for processing the photographic material as claimed in
claim 1, wherein the fine particles of the compound represented by
formula (D) in a dispersion are monodisperse.
9. A method for processing the photographic material as claimed in
claim 1, wherein the compound represented by formula (D) is present
in the light-sensitive silver halide emulsion layer which is the
closest to the support.
Description
FIELD OF THE INVENTION
The present invention relates to a silver halide photographic
material and a processing method thereof, more specifically, to a
silver halide photographic material able to provide an improved
color balance at a rapid processing and a processing method
thereof.
BACKGROUND OF THE INVENTION
As the color developing agent for use in a color developer of a
silver halide color photographic material, a great number of
N,N-dialkylparaphenylenediamine-based compounds have hitherto been
known and examples thereof include N-hydroxyalkyl-based compound
described in U.S. Pat. No. 2,108,243, British Patent 807,899 and
European Patent 410450A2 and N-sulfonamidoalkyl-based compounds
described in U.S. Pat. Nos. 2,193,015, 2,552,240 and 2,566,271. On
the other hand, in order to expedite the processing or to reduce
effects of the development waste water on environment, an
N,N-dialkylparaphenylenediamine-based color developing agent used
in a color developer is incorporated into a photographic material
as described in U.S. Pat. Nos. 4,157,915 and 5,210,007 and European
Patent 547,621A1. However, reduction in the replenishing amount
effected for the purpose of rapid processing and environmental
conservation is associated with deterioration in color balance and
an improvement therefor has been demanded.
The present invention has been accomplished on considering the
above-described circumstances.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a silver halide
photographic material suitable for rapid processing.
Another object of the present invention is to provide a
photographic material able to provide excellent color balance at
the rapid processing and a processing method thereof.
DETAILED DESCRIPTION OF THE INVENTION
The above-described objects can be achieved by silver halide
photographic materials and processing methods thereof, more
specifically,
(1) a silver halide color photographic material comprising a
support having thereon at least two light-sensitive silver halide
emulsion layers, the lowermost light-sensitive silver halide
emulsion layer and/or a light-insensitive layer adjacent thereto
containing a compound represented by formula (D): ##STR2## wherein
R.sup.1 and R.sup.2 each represents an alkyl group, an aryl group
or a heterocyclic group, R.sup.3, R.sup.4 R.sup.5 and R.sup.6 each
represents a hydrogen atom, a halogen atom or a substituent
connecting to the benzene ring through a carbon atom, an oxygen
atom, a nitrogen atom or a sulfur atom, R.sup.1 and R.sup.2,
R.sup.1 and R.sup.3, R.sup.3 and R.sup.4, R.sup.2 and R.sup.5 or
R.sup.5 and R.sup.6 may be combined to form a ring, R.sup.7
represents a hydrogen atom or forms=(T).sub.m S together with
-(T).sub.m S, T represents a timing group, m represents an integer
of 0 to 3 and S represents a protective group eliminated at the
development;
(2) a photographic material as described in (1) above wherein said
compound of formula (D) is a dispersion of fine solid;
(3) a photographic material as described in (1) above wherein the
silver halide emulsion has an iodide content of at least from 3.0
to 15 mole %;
(4) a method for processing the photographic material described in
(1) comprising processing the photographic material of (1) above
with a color developer containing a paraphenylenediamine-based
color forming developing agent; and
(5) a method for processing a photographic material as described in
(3) wherein the processing time of the color development is from 30
to 90 seconds in the method as described in (4).
Formula (D) is described below in detail.
The term "at least two light-sensitive silver halide emulsion
layers" as used in the present invention, more specifically, means
at least two layers different in color sensitivity such as blue
sensitivity, green sensitivity and red sensitivity.
In the present invention, the compound represented by formula (D)
may be used in the lowermost light-sensitive emulsion layer and/or
a light-insensitive layer adjacent thereto, however, for example,
when emulsion layers having the same color sensitivity but
different in sensitivity are present, the compound may be
preferably used in an emulsion layer closer to the support and/or a
light-insensitive layer adjacent thereto.
R.sup.1 and R.sup.2, which may be the same or different, each
represents an alkyl group, an aryl group or a heterocyclic group,
which may be substituted by an alkyl group, an alkenyl group, an
alkynyl group, a hydroxyl group, a nitro group, a carboxyl group, a
cyano group, a halogen atom, an aryl group, a heterocyclic group,
an alkoxy group, an aryloxy group, an acylamino group, an
alkylamino group, an anilino group, a ureido group, a
sulfamoylamino group, an alkylthio group, an arylthio group, an
alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group,
a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a
heterocyclic oxy group, an azo group, an acyloxy group, a
carbamoyloxy group, a silyl group, a silyloxy group, an
aryloxycarbonylamino group, an imido group, a heterocyclic thio
group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl
group or an acyl group. These groups may be further be substituted
by these groups.
More specifically, R.sup.1 and R.sup.2 each represents an alkyl
group having from 1 to 16 carbon atoms or a linear, branched or
cyclic alkyl group having from 1 to 6 carbon atoms. Examples
thereof include methyl, ethyl, propyl, isopropyl, t-butyl,
2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl,
3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl,
cyclopentyl, 2-acetoamidoethyl, 2-carboxylethyl, 2-carbamoylethyl,
3-carbamoylpropyl, hexyl, 2-hydroxypropyl, 4-hydroxybutyl,
2-carbamoylaminoethyl, 3-carbamoylaminopropyl,
4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl
and 4-nitrobutyl.
The aryl group is preferably an aryl group having from 6 to 24,
preferably from 6 to 12 carbon atoms and examples thereof include
phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a
5- or 6-membered saturated or unsaturated heterocyclic ring having
from 1 to 5 carbon atoms and containing from 1 to 4 oxygen,
nitrogen or sulfur atoms and the number and the kind of the hetero
atom constituting the ring may be either single or in a plurality.
Examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl,
2-benzotriazolyl, imidazolyl and pyrazolyl.
R.sup.1 and R.sup.2 may be combined with each other to form a ring.
There is no particular restriction on the ring formed by these and
among these, preferred are 5-, 6- and 7-membered saturated ring
constituted by elements selected from the group consisting of a
carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom.
Examples of the ring include pyrrolidino, pyperadino and
morpholino. These rings may further be substituted by a substituent
allowed for R.sup.1.
R.sup.1 and R.sup.2 each preferably represents a substituted or
unsubstituted alkyl group or may be combined to form a pyrrolidine
ring. The substituent of R.sup.1 or R.sup.2 is preferably a
hydroxyl group, a carboxyl group, a cyano group, an alkoxy group,
an acylamino group, an alkylamino group, a ureido group, a
sulfamoylamino group, an alkoxycarbonylamino group, a sulfonamido
group, a carbamoyl group, a sulfamoyl group or a sulfonyl group.
R.sup.1 and R.sup.2 each is more preferably an unsubstituted alkyl
group or an alkyl group substituted by a hydroxyl, alkoxy or
sulfonamido group.
R.sup.3, R.sup.4, R.sup.5 and R.sup.6, which may be the same or
different, each represents a hydrogen atom, a halogen atom or a
substituent connecting to the benzene ring through a carbon atom,
an oxygen atom, a nitrogen atom or a sulfur atom.
Examples of the substituent represented by R.sup.3, R.sup.4,
R.sup.5 or R.sup.6 connected through a carbon atom include an alkyl
group, an alkenyl group, an alkynyl group, an aryl group and
heterocyclic group; examples of the substituent connected through
an oxygen atom include a hydroxyl group, an alkoxy group, an
aryloxy group, a heterocyclic oxy group, an acyloxy group, a
carbamoyloxy group and a sulfonyloxy group; examples of the
substituent connected through a nitrogen atom include an acylamino
group, an amino group, an alkylamino group, an arylamino group, a
heterocyclic amino group, a ureido group, a sulfamoylamino group,
an alkoxycarbonylamino group, an aryloxycarbonylamino group, a
sulfonamido group, an imido group and a heterocyclic group; and
examples of the substituent connected through a sulfur atom include
an alkylthio group, an arylthio group and a heterocyclic thio
group. These may be further substituted by a substituent by an
alkyl group, an alkenyl group, an alkynyl group, an aryl group, a
hydroxyl group, a cyano group, a halogen atom or a substituent
formed by an oxygen atom, a nitrogen atom, a sulfur atom or a
carbon atom.
The substituent represented by R.sup.3, R.sup.4, R.sup.5 or R.sup.6
will be described below more specifically.
Examples of the halogen atom include a fluorine atom, a chloride
atom and a bromine atom.
The alkyl group is a linear, branched or cyclic alkyl group having
from 1 to 16, preferably from 1 to 6 carbon atoms and examples
thereof include methyl, ethyl, propyl, isopropyl, t-butyl,
2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl,
3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl,
cyclopentyl, 2-acetamidoethyl, 2-carboxylethyl, 2-carbamoylethyl,
3-carbamoylpropyl, hexyl, 2-hydroxypropyl, 4-hydroxybutyl,
2-carbamoylaminoethyl, 3-carbamoylaminopropyl,
4-carbamoylaminobutyl, 4-carbamoylbutyl and
2-carbamoyl-1-methylethyl.
The alkenyl group is an alkyl group having from 2 to 16 carbon
atoms and examples thereof include vinyl, 1-propenyl, 1-hexenyl and
styryl.
The alkynyl group is an alkynyl group having from 2 to 16 carbon
atoms and examples thereof include ethynyl, 1-butynyl, 1-dodecenyl
and phenylethynyl.
The aryl group is an aryl group having from 6 to 24 carbon atoms
and examples thereof include phenyl, naphthyl and
p-methoxyphenyl.
The heterocyclic group connected through the carbon atom on the
ring is a 5- or 6-membered, saturated or unsaturated heterocyclic
ring having from 1 to 5 carbon atoms and containing one or more of
an oxygen atom, a nitrogen atom and a sulfur atom and the number
and the kind of the hetero atoms constituting the ring may be
either single or in a plurality. Examples thereof include 2-furyl,
2-thienyl, 2-pyrmidinyl and 2-imidazolyl.
The alkoxy group is an alkoxy group having from 1 to 16, preferably
from 1 to 6 carbon atoms and examples thereof include methoxy,
ethoxy, 2-methoxyethoxy and 2-methanesulfonylethoxy.
The aryloxy group is an aryloxy group having from 6 to 24 carbon
atoms and examples thereof include phenoxy, p-methoxyphenoxy,
m-(3-hydroxypropionamido)phenoxy.
The heterocyclic oxy group is a 5- or 6-membered, saturated or
unsaturated heterocyclic oxy group having from 1 to 5 carbon atoms
and containing one or more of an oxygen atom, a nitrogen atom and a
sulfur atom and the number and the kind of the hetero atoms
constituting the ring may be either single or in a plurality.
Examples thereof include 1-phenyltetrazolyl-5-oxy,
2-tetrahydropyranyloxy and 2-pyridyloxy.
The acyloxy group is an acyloxy group having from 1 to 16,
preferably from 1 to 6 carbon atoms and examples thereof include
acetoxy, benzoyloxy and 4-hydroxybutanoyloxy.
The carbamoyloxy group is a carbamoyloxy group having from 1 to 16,
preferably from 1 to 6 carbon atoms and examples thereof include
N,N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and
N-phenylcarbamoyloxy.
The sulfonyloxy group is a sulfonyloxy group having from 1 to 16
carbon atoms and examples thereof include methanesulfonyloxy and
benzenesulfonyloxy.
The acylamino group is an acylamino group having from 1 to 16,
preferably from 1 to 6 carbon atoms, and examples thereof include
acetamido, 2-methoxypropionamido and p-chlorobenzoylamido.
The alkylamino group is an alkylamino group having from 1 to 16,
preferably from 1 to 6 carbon atoms and examples thereof include
N,N-dimethylamino, N,N-diethylamino and
N-(2-hydroxyethyl)amino.
The arylamino group is an arylamino group having from 6 to 24
carbon atoms and examples thereof include anilino, m-nitroanilino
and N-methylanilino.
The heterocyclic amino group is a 5- or 6-membered, saturated or
unsaturated heterocyclic amino group having from 1 to 5 carbon
atoms and containing one or more of an oxygen atom, a nitrogen atom
and a sulfur atom and the number and the kind of the hetero atom
constituting the ring may be either single or in a plurality.
Examples thereof include 2-oxazolylamino, 2-tetrahydropyranylamino
and 4-pyridylamino.
The ureido group is a ureido group having from 1 to 16, preferably
from 1 to 6 carbon atoms and examples thereof include ureido,
methylureido, N,N-diethylureido and
2-methanesulfonamidoethylureido.
The sulfamoylamino group is a sulfamoylamino group having from 0 to
16, preferably from 0 to 6 carbon atoms and examples thereof
include dimethylsulfamoylamino, methyl-sulfamoylamino and
2-methoxyethylsulfamoylamino.
The alkoxycarbonylamino group is an alkoxy-carbonylamino group
having from 2 to 16, preferably from 2 to 6 carbon atoms and
examples thereof include methoxycarbonyl-amino, ethoxycarbonylamino
and 3-methanesulfonylpropyloxy-carbonylamino.
The aryloxycarbonylamino group is an aryloxy-carbonylamino group
having from 7 to 24 carbon atoms and examples thereof include
phenoxycarbonylamino, 4-cyano-phenoxycarbonylamino and
2,6-dimethoxyphenoxycarbonylamino.
The sulfonamido group is a sulfonamido group having from 1 to 16,
preferably from 1 to 6 carbon atoms and examples thereof include
methanesulfonamido, p-toluenesulfonamido and
2-methoxyethanesulfonamido.
The imido group is an imido group having from 4 to 16 carbon atoms
and examples thereof include N-succinimido and N-phthalimido.
The heterocyclic group connected through the nitrogen atom on the
ring is a 5- or 6-membered heterocyclic ring comprising at least
one of a carbon atom, an oxygen atom and a sulfur atom and a
nitrogen atom and examples thereof include pyrrolidino, morpholino
and imidazolino.
The alkylthio group is an alkyl thio group having from 1 to 16,
preferably from 1 to 6 carbon atoms and examples thereof include
methylthio, ethylthio and 2-phenoxyethylthio.
The arylthio group is an arylthio group having from 6 to 24 carbon
atoms and examples thereof include phenylthio, 2-carboxyphenylthio
and 4-cyanophenylthio.
The heterocyclic thio group is a 5- or 6-membered, saturated or
unsaturated heterocyclic thio group containing one or more of an
oxygen atom, a nitrogen atom and a sulfur atom and the number and
the kind of the hetero atom constituting the ring may be either
single or in a plurality. Examples thereof include
2-benzothiazolylthio and 2-pyridyl-thio.
R.sup.1 and R.sup.3 or R.sup.2 and R.sup.5 may be combined to form
a ring. There is no particular restriction on the ring formed by
these and among these, preferred are 5-, 6- and 7-membered
nitrogen-containing heterocyclic ring constituted by elements
selected from the group consisting of a carbon atom, an oxygen
atom, a nitrogen atom and a sulfur atom. Examples of the ring
include tetrahydropyridine, 1,4-dihydroxazine, tetrahydropyrazine
and pyrroline. R.sup.3 and R.sup.4 or R.sup.5 and R.sup.6 may be
combined to form a ring. The ring formed by these is a 5-, 6- or
7-membered ring constituted by elements selected from the group
consisting of a carbon atom, an oxygen atom, a nitrogen atom and a
sulfur atom and examples of the ring include cyclopentene,
dihydrofuran and pyrroline.
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each is preferably a hydrogen
atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy
group having from 1 to 6 carbon atoms, an acylamino group having
from 1 to 6 carbon atoms, a ureido group having from 1 to 6 carbon
atoms, a sulfamoylamino group having from 2 to 12 carbon atoms, an
alkoxycarbonylamino group having from 1 to 6 carbon atoms or a
sulfonamido group having from 1 to 6 carbon atoms, more preferably
a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an
alkoxy group having from 1 to 6 carbon atoms or an
alkoxycarbonylamino group having from 1 to 6 carbon atoms, and most
preferably an alkyl group having from 1 or 2 carbon atoms or an
alkoxy group having from 1 to 3 carbon atoms. R.sup.3 and R.sup.5
each is preferably a hydrogen atom or combined with R.sup.1 and R2,
respectively, to form a ring. Either one of R.sup.4 and R.sup.6 is
preferably a hydrogen atom and more preferably, R.sup.4 is a
hydrogen atom and R.sup.6 is an alkyl group having from 1 or 2
carbon atoms or an alkoxy group having from 1 to 3 carbon
atoms.
m is from 0 to 3 and when m is 2 or 3, T means that different
timing groups are connected. m is preferably 1.
Among compounds represented by formula (D) of the present
invention, preferred are those represented by the following formula
(E): ##STR3## wherein R.sup.1, R.sup.2, R.sup.4, R.sup.7, T, S and
m each has the same meaning as in formula (D).
In formula (E), more preferably,
R.sup.1, R.sup.2 : an unsubstituted alkyl or hydroxyalkyl group,
R.sup.1 and R.sup.2 are combined to form a 5-membered ring, or
R.sup.1 is combined with the benzene ring to form a 5- or
6-membered ring;
R.sup.4 : an alkyl group or an alkoxy group;
R.sup.7 : H.
T in formula (D) represents a timing group and examples thereof
include those described in U.S. Pat. No. Nos. 4,146,396, 4,248,962,
4,409,323, 4,772,537 and 5,019,492, British Patent 2,096,783,
JP-A-51-146828 (the term "JP-A" as used herein means an "unexamined
published Japanese patent application") and JP-A-57-56837. When m
is in a plurality, T may be the same or different.
Preferred examples of the timing group include the following:
(1) a group using a cleavage reaction of hemiacetal and examples
thereof include those described in U.S. Pat. No. 4,146,396,
JP-A-60-249148 and JP-A-60-249149;
(2) a group causing a cleavage reaction using an intramolecular
nucleophilic substitution reaction and examples thereof include
those described in U.S. Pat. No. 4,248,962;
(3) a group causing a cleavage reaction using an electron transfer
reaction along a conjugated system and examples thereof include
those described in U.S. Pat. No. 4,409,323 and 4,421,845;
(4) a group using a cleavage reaction by hydrolysis of an ester and
examples thereof include those described West German Patent (OLS)
No. 2,626,315; and
(5) a group using a cleavage reaction of iminoacetal and examples
thereof include those described in U.S. Pat. No. 4,546,073.
S in formula (D) represents a protective group to be eliminated at
development. The protective group is eliminated by components of a
processing solution at development, such as hydroxyl ion, sulfite
ion, a color developing agent or hydroxylamine. The scission
mechanism thereof includes a direct scission such as intermolecular
nucleophilic substitution reaction or elimination reaction and an
indirect breaking such as intermolecular addition reaction or
intramolecular nucleophilic substitution following the substitution
reaction. Examples of the protective group represented by S include
a group cleaving on hydrolysis (e.g., acyl group, sulfonyl group,
sulfinyl group, aminomethyl group), a group cleaving on reverse
Michael addition reaction (e.g., 2-cyanoethyl group, 2-acylethyl
group, 2-sulfonylethyl group, 2-carbamoylethyl group,
pyrrolidine-2,5-3-yl group), a group cleaving on addition-release
reaction (e.g., uracyl group, 2-cyclohexenon-3-yl group,
maleinimido-3-yl group, 2-alkoxycarbonylethenyl group,
2-acylethenyl group), a group cleaving on intramolecular electron
transfer reaction (e.g., quinonemethide production cleaving group),
a group cleaving on intramolecular nucleophilic substitution
reaction (e.g., 3-acylpropanoyl group, 2-acyl-2,2-dialkylacetyl
group), a group blocked with a phthalide group or a saccharin group
and a group blocked with an imidomethyl group.
Of them, a group cleaving on reverse Michael addition reaction, a
group cleaving on addition-release reaction and a group cleaving on
intramolecular nucleophilic substitution reaction are preferred. A
group cleaving on addition-release reaction and a group cleaving on
intramolecular nucleophilic substitution reaction are more
preferred. Specific examples of S and -(T).sub.m S are set forth
below. In the followiing examples, a part represented by "T" shows
a T-moiety and a part represented by "S" shows a S-moiety in a
group of -(T).sub.m S. ##STR4##
Among these specific examples of the partial structure, include
(1), (3), (4), (5), (7), (8), (9), (17), (19), (22), (23), (24),
(25), (28), (31), (32) and (33) are examples of S.
Others are specific examples of -(T).sub.m S.
The compound represented by formula (D) can be produced, stored and
used not only in the form of a free amine but also of an inorganic
or organic acid salt. Examples of the inorganic or organic acid for
making a salt of the compound of formula (D) include a chloric
acid, a sulfuric acid, a phosphoric acid, p-toluenesulfonic acid, a
methanesulfonic acid and a naphthalene-1,5-disulfonic acid.
Specific examples of the blocked developing agent represented by
formula (D) of the present invention are described below but the
present invention is by no means limited to these examples.
##STR5##
The compound represented by formula (D) of the present invention is
described in the following patents and patents/literatures cited
therein: U.S. Pat. No. Nos. 2,911,410, 3,342,599, 4,426,441,
4,157,915 and 5,210,007, JP-A-53-135628, JP-A-54-79035,
JP-A-58-1139, JP-A-58-1140, JP-A-56-107236, JP-A-61-113059 and
European Patent 547621A1.
The color developing agents preferably used in developing a
photographic material containing the compound of the present
invention are described below.
P-1 N,N-Diethyl-p-phenylenediamine
P-2 2-Amino-5-(N,N-diethylamino)toluene
P-3 2-Amino-5-(N-ethyl-N-laurylamino)toluene
P-4 4-[N-Ethyl-N-(.beta.-hydroxyethyl)amino]aniline
P-5 2-Methyl-4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]-aniline
P-6
4-Amino-3-methyl-N-ethyl-N-[.beta.-(methanesulfon-amido)ethyl]aniline
P-7
N-(2-Amino-5-N,N-diethylaminophenylethyl)methane-sulfonamide
P-8 N,N-Dimethyl-p-phenylenediamine
P-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
P-10 4-Amino-3-methyl-N-ethyl-N-.beta.-ethoxyethylaniline
P-11 4-Amino-3-methyl-N-ethyl-N-.beta.-butoxyethylaniline
Preferred among these are Compounds P-5 and P-6. These
p-phenylenediamine derivatives are commonly used as a slat such as
a sulfate, a hydrochloride, a sulfite, a p-toluenesulfonate, a
nitrate or a naphthalene-1,5-disulfonate. The use amount of the
aromatic primary amine developing agent is preferably from about
0.1 to about 20 g per of the developer. The amount of the
developing agent used in combination is preferably from 1/10 to 10
moles per mole of the developing agent represented by the formula
of the present invention as long as the effect of the present
invention is not impaired.
The color developer for use in the present invention is usually
alkaline and preferably an alkaline aqueous solution having a pH of
from 9 to 12.5.
The compound of formula (D) is preferably dispersed in a form of
oil droplet or fine solid.
The dispersion method for obtaining a fine solid dispersion of the
compound represented by formula (D) may be any known grinding
method such as ball milling, vibration ball milling, planetary ball
milling, sand milling, colloidal milling, jet milling or roller
milling and the dispersion is conducted preferably using a solvent
(for example, water), more preferably a surface active agent for
dispersion. Alternatively, fine crystals may be precipitated by
dissolving the dyestuff of the present invention in an appropriate
solvent and then thereto adding a bad solvent of the dyestuff of
the present invention and also in this case, a surface active agent
for dispersion may be used. Or, the dyestuff of the present
invention may be first dissolved in a solvent under the control of
pH and then finely crystallized by changing the pH.
The compound represented by formula (D) of the present invention in
a dispersion has an average particle size of 10 .mu.m or less (
preferably 0.01 .mu.m or more), preferably 1 .mu.m or less, more
preferably 0.5 .mu.m or less and if desired, 0.1 .mu.m or less. The
fine particles are preferably monodispersed.
In dispersing, the compound of formula (D) m ay be dispersed as it
is without subjecting it to any pretreatment. In this case, a solid
in a wet state obtained during the synthesis of the compound is
preferably used for the dispersion.
If desired, heat treatment may be conducted before and/or after the
dispersion and in order to conduct heat treatment more effectively,
the heat treatment is preferably conducted at least after
dispersion.
The heating method is not particularly limited as long as heat is
applied to the solid compound of formula (D) and the temperature is
preferably 40.degree. C. or higher but the upper bound is not
particularly limited as long as the dyestuff is not decomposed and
preferably 250.degree. C. or lower. The heating temperature is more
preferably from 50.degree. to 150.degree. C.
The heating period is not particularly limited as long as the
compound of formula (D) is not decomposed and it is usually from 15
minutes to 1 week, preferably from 1 hour to 4 days.
The heating treatment is preferably conducted in a solvent to
achieve effective heating and the kind of the solvent is not
particularly restricted as long as it does not substantially
dissolve the compound of formula (D). Examples of the solvent
include water, alcohols (e.g., methanol, ethanol, isopropyl
alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol,
diethylene glycol, ethyl cellosolve), ketones (e.g., acetone,
methyl ethyl ketone), esters (e.g., ethyl acetate, butyl acetate),
alkylcarboxylic acids (e.g., acetic acid, propionic acid), nitrites
(e.g., acetonitrile) and ethers (e.g., dimethoxyethane, dioxane,
tetrahydrofuran).
When an organic carboxylic acid is present together in the heat
treatment, the objects which the present invention intends can be
attained more effectively. Examples of the organic carboxylic acid
include alkylcarboxylic acids (e.g., acetic acid, propionic acid),
carboxymethyl celluloses (CMS) and arylcarboxylic acids (e.g.,
benzoic acid, salicylic acid).
In the case where the organic carboxylic acid is used as a solvent,
it can be used in an amount of from 0.5 to 100 times the weight of
the compound represented by formula (D). In the case where an
organic carboxylic acid is used with a solvent other than an
organic carboxylic acid, the organic carboxylic acid can be used at
a weight ratio of from 0.05 to 100% to the compound of formula
(D).
The compound represented by formula (D) can be used in any
effective amount, and it is preferably used in an amount such that
a colored dye can provide a sufficient density. Although the
addition amount may vary depending upon developing agent releasing
efficiency at development, silver developability or coloring
efficiency, it is preferably from 2.times.10.sup.-2 mmole/m.sup.2
to 10 mmole/m.sup.2, more preferably from 1.times.10.sup.-1
mmole/m.sup.2 to 6 mmole/m.sup.2.
The color developer may contain a compound directly preserving the
aromatic primary amine color developing agent such as various
hydroxylamines described in JP-A-63-5341, JP-A-63-106655 and
JP-A-4-144446, hydroxamic acids described in JP-A-63-43138,
hydrazines or hydrazides described in JP-A-63-146041, phenols
described in JP-A-63-44657 and JP-A-63-58443,
.alpha.-hydroxyketones or (-aminoketones described in JP-A-63-44656
or various saccharides described in JP-A-63-36244. Also, in
combination with the above-described compound, monoamines described
in JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-146040,
JP-A-63-27841 and JP-A-63-25654, diamines described in
JP-A-63-30845, JP-A-63-14640 and JP-A-63-43139, polyamines
described in JP-A-63-21647, JP-A-63-26655 and JP-A-63-44655,
nitroxy radicals described in JP-A-63-53551, alcohols described in
JP-A-63-43140 and JP-A-63-53549, oximes described in JP-A-63-56654
or tertiary amines described in JP-A-63-239447 can be used. The
color developer may also contain, if desired, other preservatives
such as various metals described in JP-A-57-44148 and
JP-A-57-53749, salicylic acids described in JP-A-59-180588,
alkanolamines described in JP-A-54-3582, polyethyleneimines
described in JP-A-56-94349 or aromatic polyhydroxy compounds
described in U.S. Pat. No. 3,746,544. In particular, when a
hydroxylamine is used, the above-described alkanolamine or aromatic
polyhydroxy compound is preferably used in combination.
More preferred preservatives are hydroxylamines represented by
formula (I) of JP-A-3-144446 and among these, still more preferred
are compounds having a methyl group, an ethyl group, a sulfo group
or a carboxyl group. The preservative is added in an amount of from
20 to 200 mmole, preferably from 30 to 150 mmole per of the color
developer.
The developer for a photographic material for printing preferably
contains chloride ions in an amount of from 3.0.times.10.sup.-2 to
1.5.times.10.sup.-1 mole/liter, more preferably from
3.5.times.10.sup.-2 to 1.0.times.10.sup.-1 mole/liter. The chloride
ion concentration exceeding 1.5.times.10 .sup.-1 mole/liter is
deficient in that the development is retarded and not preferred in
attaining the objects of the present invention to achieve a high
maximum density by a rapid processing. On the other hand, the
chloride ion concentration less than 3.0.times.10.sup.-2 mole/liter
is not preferred in view of prevention of fogging.
The color developer of the present invention preferably contains
bromide ions in an amount of from 0.5.times.10.sup.-5 to
1.0.times.10.sup.-3 mole/liter, more preferably from
3.0.times.10.sup.-5 to 5.times.10.sup.-4 mole/liter. If the bromide
ion concentration exceeds 1.0.times.10.sup.-3 mole/liter, the
development is retarded and the maximum density and sensitivity are
reduced, whereas if it is less than 0.5.times.10.sup.-5 mole/liter,
fogging cannot be sufficiently prevented.
The chloride ion or bromide ion may be added directly to the color
developer or may be eluted from a photographic material to the
color developer during development.
When the ion is added directly to the color developer, the chloride
ion-providing substance includes sodium chloride, potassium
chloride, ammonium chloride, lithium chloride, magnesium chloride
and calcium chloride. Also, the chloride ion may be supplied from a
fluorescent brightening agent added in the color developer. The
bromide ion-providing substance includes sodium bromide, potassium
bromide, ammonium bromide, lithium bromide, calcium bromide and
magnesium bromide.
When the ion is eluted from a photographic material to the
developer, the chloride or bromide ion may be supplied either from
an emulsion or from material other than the emulsion.
In addition, various additives described in JP-A-3-144446 may be
used in the color developer. For example, as a buffering agent for
retaining the pH, carbonic acids, phosphoric acids, boric acids and
hydroxybenzoic acids described in idem, page (9), may be used. The
pH of the color developer is preferably kept at from 9.0 to 12.5,
more preferably from 9.5 to 11.5 by using a buffering agent as
described above.
The antifoggant includes halide ions and organic antifoggants
described in idem, page (10). In the case where the developing
agent concentration in the color developer is high as 20
mmole/liter or more or the development is processed at high
temperatures higher than 40.degree. C., the higher bromide ion
concentration is preferred and it is preferably from 17 mmole/liter
to 60 mmole/liter. If desired, the halogen is removed by using an
ion exchange resin or an ion exchange membrane to control the
concentration to lie in a preferred range.
As the chelating agent, an aminopolycarboxylic acid, an
aminopolyphosphonic acid, an alkylphosphonic acid or a
phosphonocarboxylic acid is preferably used. Representative
examples thereof include ethylenediaminetetraacetic acid,
nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid,
1-hydroxyethylidene-1,l-diphospN,N,N acid,
nitrilo-N,N,N-trimethylenephosphonic acid,
ethylenediamine-N,N,N,N-tetramethylenephosphonic acid,
ethylenediamine-di(o-hydroxy-phenylacetic acid) and salts thereof.
Also, compounds having biodegradability are preferably used as the
chelating agent. Examples thereof include those described in
JP-A-63-146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267751,
JP-A-2-229146, JP-A-3-186841, German Patent 3,739,610 and European
Patent 468325.
Further, a development inhibitor such as benz-imidazoles,
benzothiazoles and mercapto compounds, a development accelerator
such as benzyl alcohol, polyethylene glycol, quaternary ammonium
salts and amines, a dye-forming coupler, a competitive coupler, an
auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a
viscosity-providing agent or various surface active agents such as
an alkylsulfonic acid, an arylsulfonic acid, an aliphatic
carboxylic acid and an aromatic carboxylic acid may be added, if
desired.
The color developer may freely contain a development accelerator,
if desired.
Examples of the development accelerator include thioether compounds
described in JP-B-37-16088 (the term "JP-B" as used herein means an
"examined Japanese patent publication"), JP-B-37-5987,
JP-B-38-7826, JP-B-44-12380, JP-B-45-9091 and U.S. Pat. No.
3,813,247; p-phenylenedimaine compounds described in JP-A-52-49829
and JP-A-50-15554; quaternary ammonium salts described in
JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429;
amine compounds described in U.S. Pat. Nos. 2,494,903, 3,128,182,
4,230,796 and 3,253,919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546,
2,596,926 and 3,582,346; polyalkylene oxides described in
JP-B-37-1600, JP-B-42-25201, U.S. Pat. No. 3,128,183,
JP-B-41-11431, JP-B-42-23883 and U.S. Pat. No. 3,532,501;
1-phenyl-3-pyrazolidones; and imidazoles.
In the case where a photographic material for photographing is
processed in the method of the present invention, the replenishing
amount of the color developer is preferably 550 ml/m.sup.2 or less
in view of the above-described objects, more preferably 450
ml/m.sup.2 or less and most preferably from 80 to 400 ml/m.sup.2.
The replenishing amount may be 300 ml or less when the bromide ion
concentration in the replenisher is reduced or the bromide ion is
not contained therein. In the case of a photographic material for
printing, the replenishing amount of the color developer is
suitably from 20 to 600 ml, preferably 30 to 200 ml, more
preferably from 40 to 100 ml, per m.sup.2 of the photographic
material.
The processing temperature with the color developer is, in the case
of a photographic material for photographing, preferably 35.degree.
C. or higher, more preferably from 40.degree. to 50.degree. C. In
the case of a photographic material for printing, it is from
20.degree. to 50.degree. C., preferably from 30.degree. to
45.degree. C. and most preferably from 37.degree. to 42.degree.
C.
In the case of a photographic material for printing, the developer
preferably contains substantially no benzyl alcohol.
In the case of a photographic material for printing, in order to
suppress fluctuation in photographic properties accompanying a
continuous processing or to achieve the effect of the present
invention, the developer preferably contains substantially no
sulfite ion (the term "contain substantially no sulfite ion" as
used herein means that the sulfite ion concentration is
3.0.times.10.sup.-3 mole/liter or less). The sulfite ion is
preferably contained in an amount of 1.0.times.10.sup.-3 mole/liter
and most preferably it is not contained at all. However, here, a
slight amount of sulfite ions is excluded, which is used to prevent
oxidation of a processing agent kit where the developing agent is
concentrated before formulation into a practical processing
solution. The developer is more preferably contains substantially
no hydroxylamine (the term "contain substantially no hydroxylamine"
as used here means that the hydroxylamine concentration is
5.0.times.10.sup.-3 mole/liter or less) so as to suppress
fluctuation in photographic properties accompanying the change in
concentration of hydroxylamine. The developer most preferably
contains no hydroxylamine at all.
The processing solution is preferably prevented from evaporation or
air oxidation. The contact area between a photographic processing
solution and air in a processing tank can be expressed by an
opening ratio defined below.
The opening ratio as defined above is preferably 0.05 cm.sup.-1 or
less, more preferably from 0.0005 to 0.01 cm.sup.-1. The opening
ratio can be reduced, for example, by providing a shielding
material such as a floating lid on the surface of the photographic
processing solution in the processing tank, by using a movable lid
described in JP-A-1-82033 or by a slit development method described
in JP-A-63-216050. Also, the processing solution in a replenisher
tank or a processing tank for the color developer is preferably
shielded by a high boiling point organic solvent or a polymer
compound to reduce the contact area with air. Liquid paraffin or
organosiloxane is preferably used to this effect. The reduction in
opening ratio can be applied either to color development or to
black-and-white development and also to any subsequent step such as
bleaching, bleach-fixing, fixing, water washing or
stabilization.
The developer can be regenerated and used again. The regeneration
of the developer means to increase activation of the developer by
applying an anionic exchange resin or electrodialysis to the used
developer or adding processing chemicals called a regenerant and to
use it again as a processing solution. In this case, the
regeneration ratio (the proportion of the overflow in the
replenisher) is preferably 70% or more, more preferably 90% or
more.
The regeneration is preferably conducted by using an anion exchange
resin. Preferred examples of the composition for the anionic
exchange resin and the regeneration method using the resin include
those described in Diaion Manual (I), published by Mitsubishi
Chemical Industries, Ltd. (14th version, 1986). Among anion
exchange resins, resins having compositions described in JP-A-2-952
and JP-A-1-281152 are preferred.
The photographic material after color development is usually
subjected to desilvering. The desilvering fundamentally comprises
bleaching and fixing and is conducted by bleach-fixing where
bleaching and fixing are conducted simultaneously or a combination
of these processings.
Examples of the bleaching agent include iron salts; compounds of a
polyvalent metal such as iron(III), cobalt(III), chromium(IV) or
copper(II); peracids; quinones and nitro compounds. Representative
examples of the bleaching agent include iron chloride,
ferricyanide, bichromate, an organic complex salt of iron(III)
(e.g., a metal complex salt of an aminopolycarboxylic acid such as
ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic
acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
1,3-diaminopropanetetraacetic acid or glycol ether
diaminetetraacetic acid), persulfate, bromate, permanganate and
nitrobenzene. Among these, preferred are an aminopolycarboxylic
acid iron(III) complex salt and its salt as described in
JP-A-3-144446, page (11) and examples thereof include ferric salts
of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic
acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
1,3-diaminopropanetetraacetic acid or glycol ether
diaminetetraacetic acid. In addition, as the bleaching agent,
complex salts of a citric acid, a tartaric acid or malic acid may
be used. Among these, more preferred are aminopolycarboxylic acid
iron(III) complex salts including an ethylenediaminetetraacetic
acid iron(III) complex salt and a 1,3-diaminopropanetetraacetic
acid iron(III) complex salt. The aminopolycarboxylic acid iron(III)
complex salt is particularly useful in either a bleaching solution
or bleach-fixing solution.
The bleaching or bleach-fixing solution or a prebath thereof may
contain a bleaching accelerator, if desired. Specific examples of
useful bleaching accelerators include those described in the
following patent specifications: compounds having a mercapto group
or disulfide bond described in U.S. Pat. No. 3,893,858, West German
Patent 1,290,812, JP-A-53-95630 and Research Disclosure, No. 17129
(July, 1978); thiazolidine derivatives described in JP-A-50-140129;
thiourea derivatives described in U.S. Pat. No. 3,706,561; iodide
salts described in JP-A-58-16235; polyoxyethylene compounds
described in West German Patent 2,748,430; polyamine compounds
described in JP-B-45-8836; and bromide ions. Among these, compounds
having a mercapto group or a disulfide group are preferred due to
their large acceleration effect and compounds described in U.S.
Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630
are particularly preferred. Also, compounds described in U.S. Pat.
No. 4,552,834 are preferred. The bleaching accelerator may be added
to the photographic material. The bleaching accelerator is
particularly effective when a color photographic material for
photographing is bleach-fixed.
Other than the bleaching agent, a rehalogenation agent or a pH
buffer described in JP-A-3-144446, page (12) or known additives may
be used in the desilverization bath.
In addition to the above-described compounds, the bleaching or
bleach-fixing solution preferably contains an organic acid for the
purpose of preventing bleaching stains. A particularly preferred
organic acid is a compound having an acid dissociation constant
(pKa) of from 2 to 6 and specific examples thereof include acetic
acid, propionic acid, hydroxyacetic acid, succinic acid, maleic
acid, glutaric acid, fumaric acid, malonic acid and adipic acid,
with succinic acid, maleic acid and glutaric acid being more
preferred.
The bleaching solution or bleach-fixing solution usually has a pH
of from 4.0 to 8.0 but the processing may be conducted at a lower
pH for expediting the processing.
Examples of the fixing agent used in the fixing or bleach-fixing
solution include thiosulfates, thiocyanates, thioether-based
compounds, thioureas and a large quantity of iodide salts, and
among these, a thiosulfate is commonly used and ammonium
thiosulfate can be most widely used. A combination use of a
thiosulfate with a thiocyanate, a thioether compound or a thiourea
is also preferred.
Preferred examples of the preservative for the fixing or
bleach-fixing solution include sulfites, bisulfites, carbonyl
bisulfite adducts and sulfinic acid compounds described in European
Patent 294769A. Further, the fixing or bleach-fixing solution
preferably contains a chelating agent such as various
aminopolycarboxylic acids or organic phosphonic acids for the
purpose of stabilization of the solution. Preferred examples of the
chelating agent include 1-hydroxyethylidene-1,1-diphosphonic acid,
ethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid),
nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic
acid, diethylenetriaminepentaacetic acid,
cyclohexanediamine-tetraacetic acid and
1,2-propylenediaminetetraacetic acid. Among these, more preferred
are 1-hydroxyethylidene-1,1-diphosphonic acid and
ethylenediaminetetraacetic acid.
The fixing solution or bleach-fixing solution preferably contains a
compound having a pKa of from 6.0 to 9.0 for adjusting the pH. For
example, an imidazole such as imidazole, 1-methylimidazole,
1-ethylimidazole or 2-methylimidazole is preferably added in an
amount of from 0.1 to 10 mole/liter.
The imidazole compound includes imidazoles and derivatives thereof
and preferred examples of the substituent therefor include an alkyl
group, an alkenyl group, an alkynyl group, an amino group, a nitro
group and a halogen atom. The alkyl, alkenyl or alkynyl group may
be further substituted by an amino group, a nitro group or a
halogen atom. The total carbon number of the substituent for the
imidazole is preferably from 1 to 6 and the substituent is most
preferably a methyl group.
Specific examples of the imidazole compound include the following
but the imidazole compound is by no means limited to these:
imidazole, 1-methylimidazole, 2-methyl-imidazole,
4-methylimidazole, 4-(2-hydroxyethyl)-imidazole, 2-ethylimidazole,
2-vinylimidazole, 4-propylimidazole, 4-(2-aminoethyl)imidazole,
2,4-dimethylimidazole and 2-chloroimidazole. Among these, preferred
are imidazole, 2-methylimidazole and 4-methylimidazole and most
preferred is imidazole.
The fixing solution or the bleach-fixing solution may further
contains various fluorescent brightening agents, defoaming agents,
surface active agents, polyvinylpyrrolidone or methanol.
The replenishing amount for the fixing solution or the
bleach-fixing solution in the processing using a replenishing
system is preferably from 100 to 3,000 ml, more preferably from 300
to 1,800 ml, per m.sup.2 of the photographic material. The
bleach-fixing solution may be replenished by a bleach-fixing
replenisher or overflows of the bleaching solution and the fixing
solution may be used therefor as described in JP-A-61-143755 and
Japanese Patent Application No. 2-216389.
The total processing time in the desilvering of a photographic
material for photographing consisting of bleaching, bleach-fixing
and fixing is preferably from 30 seconds to 3 minutes, more
preferably from 45 seconds to 2 minutes. The processing temperature
is from 30.degree. to 60.degree. C., preferably from 35.degree. to
55.degree. C.
The processing solution having a bleaching ability is particularly
preferably aerated at the processing because the photographic
properties can be very stably retained. The aeration can be
conducted using a means known in the art and for example, air is
blown into the processing solution having a bleaching ability or
air is absorbed thereinto using an executer.
The blowing of air is preferably conducted by releasing air into
the solution through a diffusion tube having fine pores. The
diffusion tube is widely used, for example, in an aeration tank for
the activated sludge processing. With respect to the aeration,
Z-121, Using Process C-41, 3rd version, pages BL-l to BL-2,
published by Eastman Kodak Co. (1982) can be referred to. In the
processing using a processing solution having a bleaching ability
of the present invention, the agitation is preferably intensified
and for the intensification, JP-A-3-33847, page 8, right upper
column, line 6 to left lower column, line 2 can be referred to
without any modification.
The processing solution having a bleaching ability can be subjected
to silver recovery by known methods and the regenerated solution
after the silver recovery can be again used. For the silver
recovery, electrolysis (described in French Patent 2,299,667),
precipitation (described in JP-A-52-73037 and German Patent No.
2,331,220), ion exchange method (described in JP-A-51-17114 and
German Patent No. 2,548,237) and metal substitution (described in
British Patent 1,353,805) are effective. The silver recovery is
preferably conducted on the in-line of the tank solution because
the rapid processing aptitude is further improved.
The overflow of used processing solution having a bleaching ability
after processing is recovered and modified in the composition by
adding components and can be used again. This way of using is
usually called regeneration and the regeneration is also preferably
effected in the present invention. With respect to the details of
regeneration, Fuji Film Processing Manual, Fuji Color Negative
Film, CN-16 Processing, published by Fuji Photo Film Co., Ltd., pp.
39-40 (revised in August, 1990) can be referred to.
The kit for preparing a processing solution having a bleaching
ability of the present invention may be either liquid or powder and
in the case where an ammonium salt is eliminated, since almost all
raw materials are supplied as powder and the hygroscopicity is low,
a powder form is easy to produce.
The above-described kit for regeneration is preferably in the form
of powder from in view of reduction in waste amount because it
requires no excess of water and can be added directly.
The processing solution having a bleaching ability can be
regenerated according to the methods described in Shashin Koqaku no
Kiso--Gin'en Shashin Hen, complied by Nippon Shashin Gakkai, issued
by Corona Sha (1979), other than the above-described aeration. More
specifically, electric field regeneration and also regeneration of
a bleaching solution by bromic acid, chlorous acid, bromine,
bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide
using a catalyst, bromous acid or ozone may be used.
In the electric field regeneration, a cathode and an anode are
placed in the same bleaching bath or an anode tank and a cathode
tank are provided as separate baths using a diaphragm to effect
regeneration, or a bleaching solution, a developer and/or a fixing
solution are simultaneously regenerated also using a diaphragm.
The fixing solution and the bleach-fixing solution are regenerated
by the electrolytic reduction of silver ions accumulated. It is
also preferred in view of keeping the fixing performance to remove
halogen ions accumulated by means of an anionic exchange resin.
In desilverization, the stirring is preferably intensified as
highly as possible. Specific examples of the method for
intensifying stirring include a method comprising colliding a jet
stream of a processing solution against the emulsion surface of the
photographic material described in JP-A-62-183460, a method for
increasing the stirring effect using a rotary means described in
JP-A-62-183461, a method for increasing the stirring effect by
causing turbulence on the emulsion surface while moving the
photographic material with putting the emulsion surface into
contact with a wire blade provided in the solution, and a method
for increasing the circulative flow rate of the entire processing
solutions. Such a means for intensifying the stirring is effective
in any of the bleaching solution, bleach-fixing solution or fixing
solution. The intensification of stirring is considered to increase
the supply rate of the bleaching agent or fixing agent into the
emulsion layer and as a result, to increase the desilverization
rate. The above-described means for intensifying stirring is more
effective when a bleaching accelerator is used and in this case,
the acceleration effect can be outstandingly increased or the
inhibition of fixing due to the bleaching accelerator can be
eliminated.
The automatic developing machine used for the photographic material
of the present invention preferably comprises a transportation
means of a photographic material described in JP-A-60-191257,
JP-A-60-191258 and JP-A-60-191259. As described in JP-A-60-191257
above, the transportation means can extremely decrease the amount
of a processing solution carried over from a previous bath to a
post bath and provides a great effect in preventing the
deterioration in performance of the processing solution. Such an
effect is particularly useful in reducing the processing time or
decreasing the replenishing amount of a processing solution in each
step.
The photographic material is generally subjected to water washing
after desilvering. The water washing may be replaced by
stabilization. In such a stabilization processing, any of known
methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345
can be used. A water washing-stabilization may also be conducted
where a stabilization bath containing a dye stabilizer and a
surface active agent is used as the final bath.
The water-washing solution and the stabilizing solution may contain
a hard water softening agent such as inorganic phosphoric acid,
polyaminocarboxylic acid and organic aminophosphonic acid.
The amount of washing water in the water washing step can be set
over a wide range according to the characteristics (e.g., materials
used such as coupler) or use of the photographic material, the
solution temperature, the number (stage) of tanks, the replenishing
system such as countercurrent or co-current, or other various
conditions. The stage number is preferably from 2 to 4. The
replenishing amount is from 1 to 50 times, preferably from 1 to 30
times, more preferably from 1 to 10 times the amount carried over
from the previous bath per unit area. For further effectively
reducing the replenishing amount, a multi-chamber water washing or
stabilization may be preferably used where the water washing or
stabilization bath is divided by a partition wall and the
photographic material passes through the slit portion such as a
wiper blade and is processed in the solution without being exposed
to air at all.
According to the above-described multi-stage countercurrent system
or a multi-chamber water washing system, the amount of washing
water may be greatly reduced but due to the increase in residence
time of water in the tank, a problem is caused that bacteria
proliferate and the floats generated adhere to the photographic
material. In order to solve such a problem, a method for reducing
calcium ions or magnesium ions described in JP-A-62-288838 can be
very effectively used. The use of water which is previously
sterilized by a sterilant such as chlorinated sodium isocyanurate
is also effective. Further, isothiazolone compounds and
thiabendazoles described in JP-A-57-8542, known chlorine-based
germicides, benzotriazoles or germicides described in Hiroshi
Horiguchi, Bokin, Bobai-Zai no Kagaku, Sankyo Shuppan (1986),
Biseibutsu no Mekkin, Sakkin, Bobai-Gilutsu compiled by Eisei
Gijutsu Kai, issued by Kogyo Gijutsu Kai (1982), and Bokin-Bobai
Zai Jiten compiled by Nippon Bokin Bobai Gakkai (1986) can be also
used.
The washing water or stabilizing solution has a pH of from 4 to 9,
preferably 5 to 8. The temperature and the processing time may be
established variously according to the characteristics and use of
the photographic material but commonly they are from 15.degree. to
45.degree. C. and from 10 seconds to 10 minutes, preferably from
25.degree. to 40.degree. C. and from 15 seconds to 5 minutes,
respectively. The photographic material of the present invention
can be processed directly by a stabilizing solution in place of the
above-described water washing. In such a stabilization processing,
any known methods described in JP-A-57-8543, JP-A-58-14834 and
JP-A-60-220345 can be used.
The stabilizing solution also contains a compound able to stabilize
a dye image, for example, aldehydes such as formalin and
m-hydroxybenzaldehyde, formaldehyde bisulfite adducts,
hexamethylenetetramine and derivatives thereof, hexahydrotriazine
and derivatives thereof, dimethylolurea, N-methylol compounds such
as N-methylolpyrazole, an organic acid or a pH buffering agent. The
addition amount of these compounds is preferably from 0.001 to 0.02
mole per liter of the stabilizing solution but the free
formaldehyde concentration is preferably lower for reducing the
diffusion of formaldehyde gas. In view of this point, preferred
examples of the dye image stabilizer include
m-hydroxy-benzaldehyde, hexamethylenetetramine, N-methylolazoles
such as N-methylolpyrazole described in JP-A-4-270344 and
azolylmethylamines such as
N,N'-bis(1,2,4-triazole-l-ylmethyl)piperazine described in
JP-A-4-313753. In particular, a combination use of an azole such as
1,2,4-triazole described in JP-A-4-359249 (corresponding to
European Patent Publication No. 619190A2) and an azolylmethylamine
or a derivative thereof such as
1,4-bis(1,2,4-triazole-1-ylmethyl)piperazine is preferred because
the image stability is high and the formaldehyde vapor pressure is
low. Further, it is preferred that the stabilizing solution
additionally contains, if desired, an ammonium compound such as
ammonium chloride or ammonium sulfite, a metal compound such as Bi
or Al, a fluorescent brightening agent, a hardening agent, an
alkanolamine described in U.S. Pat. No. 4,786,583 or a preservative
able to be used in the above-described fixing solution or
bleach-fixing solution such as a sulfinic acid compound described
in JP-A-1-231051.
The washing water or stabilizing solution may contain various
surface active agents so as to prevent water droplet unevenness at
the drying of a processed photographic material. Among surface
active agents, a nonionic surface active agent is preferably used
and an alkylphenol-ethylene oxide adduct is more preferred. The
alkylphenol is more preferably octyl, nonyl, dodecyl or
dinonylphenol and the addition molar number of the ethylene oxide
is particularly preferably from 8 to 14. Also, a silicone-based
surface active agent providing a high defoaming effect is
preferably used.
The washing water or stabilizing solution preferably contains
various chelating agents. Preferred examples of the chelating agent
include an aminopolycarboxylic acid such as
ethylenediaminetetraacetic acid or diethylenetriaminepenta- acetic
acid, an organic phosphonic acid such as 1-hydroxy-
ethylidene-1,1-diphosphonic acid, N,N,N'-trimethylene-phosphonic
acid or diethylenetriamine-N,N,N',N'-tetra-methylenesulfonic acid
and a hydrolysate of a maleic anhydride polymer described in
European Patent 345172A1.
The overflow resulting from replenishment of the above-described
washing water and/or stabilizing solution can be re-used in the
step such as desilvering.
In the processing using, for example, an automatic developing
machine, when each processing solution described above is
concentrated due to evaporation, water, a compensatory solution or
a replenisher for a processing solution is preferably supplied in
an appropriate amount to correct the concentration due to
evaporation. The water supplying method is not particularly
restricted but specifically, preferred are a method for supplying
water described in JP-A-1-254959 and JP-A-1-254960 where a monitor
water tank is provided separately from the bleaching tank, the
evaporation amount of water in the monitor water tank is
determined, the evaporation amount of water in the bleaching tank
is calculated from the evaporation amount of water determined above
and water is supplied to the bleaching tank in proportion to the
evaporation amount calculated and a method for correcting
evaporation using a liquid level sensor or an overflow sensor
described in JP-A-3-248155, JP-A-3-249644, JP-A-3-249645 and
JP-A-3-249646. The water for correcting the evaporated amount of
each processing solution may be tap water but preferably deionized
water or sterilized water which is preferably used in the
above-described water washing.
The washing water and/or stabilizing water treated with a reverse
osmosis membrane may be effectively used. The material for the
reverse osmosis membrane may be cellulose acetate, crosslinked
polyamide, polyether, polysulfone, polyacrylic acid or polyvinylene
carbonate.
The pressure for feeding a solution in using such a membrane is, in
view of stain-preventing effect and prevention of reduction in the
penetrated water amount, preferably from 2 to 10 kg/cm.sup.2, more
preferably from 3 to 7 kg/cm.sup.2.
The treatment with a reverse osmosis membrane is preferably applied
to water in the second or subsequent tanks for water washing and/or
stabilization in such a multi-stage countercurrent system. More
specifically, in the case of a two-tank structure, water in the
second tank, in the case of a three-tank structure, water in the
second or third tank, and in the four-tank structure, water in the
third or fourth tank is treated with a reverse osmosis membrane and
the penetrated water is returned to the same tank (the tank where
water for the reverse osmosis membrane treatment is sampled,
hereinafter referred to as a "sampling tank") or to the subsequent
water washing and/or stabilization tank. The concentrated washing
water and/or stabilizing solution may also be returned to the
bleach-fixing bath positioned at the upper side than the sampling
tank.
Each processing solution is preferably used at a temperature of
from 10.degree. to 50.degree. C. In general, the standard
temperature is from 33.degree. to 380C. but higher temperatures may
be used for accelerating the processing or reducing the processing
time or lower temperatures may also be used for improving the image
quality or improving stability of the processing solution.
Each processing solution may be commonly used for processing two or
more kinds of photographic materials. For example, a color negative
film and a color paper may be processed using the same processing
solutions and thereby the cost of the processor may be reduced or
the processing may be simplified.
The present invention can be applied to various color photographic
materials such as color negative film for general purpose or
movies, color reversal film for slide or television, color paper,
color positive film and color reversal paper. Also, it is
preferably used for a film unit with lens described in JP-B-2-32615
and JP-B-U-3-39784.
The photographic material may go if it comprises on a support at
least one light-sensitive emulsion layer. A typical example thereof
is a silver halide photographic material having at least one
light-sensitive layer consisting of a plurality of silver halide
emulsion layers having substantially the same color sensitivity but
different in light sensitivity. In the above-described
light-sensitive layer is a unit light-sensitive layer having color
sensitivity to any one of blue light, green light and red light and
in the case of a multi-layer silver halide color photographic
material for photographing, the unit light-sensitive layer
generally has a layer arrangement such that a red-sensitive layer,
a green-sensitive layer and a blue-sensitive layer are provided in
this order from the support side. However, the above-described
arrangement order may be reversed depending on the purpose or
layers having the same certain color sensitivity may be interpcolo
by a layer having color sensitivity different therefrom. A
light-insensitive layer may also be provided between silver halide
light-sensitive layers described above or as an uppermost or
lowermost layer. These layers may contain couplers, DIR compounds
or color mixing inhibitors which will be described later. The
silver halide emulsion layers in a plurality constituting each unit
light-sensitive layer is preferably arranged such that two layers
consisting of a high sensitive emulsion layer and a low sensitive
emulsion layer are provided so that the light sensitivity becomes
lower in sequence towards the support as described in DE 1,121,470
or British Patent 923,045. Or, a layer arrangement may also be
taken as described in JP-A-57-112751, JP-A-62-200350,
JP-A-62-206541 and JP-A-62-206543 where a low sensitive emulsion
layer is provided farther from the support and a high sensitive
emulsion layer is provided closer to the support.
Specific examples of the layer arrangement from the farthest side
towards the support include an order of a low sensitive
glue-sensitive layer (BL)/a high sensitive blue-sensitive layer
(BH)/a high sensitive green-sensitive layer (GH)/a low sensitive
green-sensitive layer (GL)/a high sensitive red-sensitive layer
(RH)/a low sensitive red-sensitive layer (RL), an order of
BH/BL/GL/GH/RH/RL and an order of BH/BL/GH/GL/RL/RH.
Also, as described in JP-B-55-34932, a blue-sensitive
layer/GH/RH/GL/RL may be arranged in this order from the farthest
side towards the support. Further, as described in JP-A-56-25738
and JP-A-62-63936, a blue-sensitive layer/GL/RL/GH/RH may be
arranged in this order from the farthest side towards the
support.
The light-sensitive layer may consist of three layers different in
the light sensitivity as described in JP-B-49-15495 where a silver
halide emulsion layer having the highest light sensitivity is
provided as an upper layer, a silver halide emulsion layer having a
light sensitivity lower than that of the upper layer as a middle
layer and a silver halide emulsion layer having a light sensitivity
lower than that of the middle layer as a lower layer so that the
light sensitivity is lowered in sequence towards the support. Even
in the case where the light-sensitive layer consists of three
layers different in the light sensitivity, as described in
JP-A-59-202464, a middle-sensitive emulsion layer/a high-sensitive
emulsion layer/a low-sensitive emulsion layer may be provided in
this order from the farthest side towards the support in the same
color sensitive layers. In addition, an order of a high sensitive
emulsion layer/a low sensitive emulsion layer/a middle sensitive
emulsion layer or an order of a low sensitive emulsion layer/a
middle sensitive emulsion layer/a high sensitive emulsion layer may
also be used. In the case of four or more layer structure, the
layer arrangement may also be changed as described above.
In order to improve color reproducibility, it is preferred to
provide adjacent to or in the vicinity of the main light sensitive
layer such as BL, GL or RL a donor layer (CL) having an interlayer
effect and being different in the light sensitivity distribution
from the main light-sensitive layer described in U.S. Pat. Nos.
4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448 and
JP-A-63-89850.
In a general photographic material for printing (i.e., color
printing paper), silver halide emulsion grains may be spectrally
sensitized in the above-described order of color forming layers by
a blue-sensitive, green-sensitive or red-sensitive spectral
sensitizing dye or may be coated on the support in the order
described above. However, a different order may also be used. More
specifically, in some cases, a light-sensitive layer containing
silver halide grains having the largest average grain size is
preferably provided as the uppermost layer in view of rapid
processing or in some cases, the magenta color-forming
light-sensitive layer is preferably provided as the lowermost layer
in view of storability under light irradiation.
Also, the light-sensitive layer and the color forming hue may be
free of the above-described correlation or at least one
infrared-sensitive silver halide emulsion may be used.
The silver halide used in the photographic material for
photographing is preferably a silver halide, such as silver
iodobromide, silver iodochloride, silver iodochlorobromide, having
a silver iodide content of about 30 mole % or less based on silver
halide, more preferably a silver halide, such as silver
iodobromide, silver iodochlorobromide, having a silver iodide
content of from about 2 to about 15 mole %, more preferably from 3
to 15 mole % based on silver halide.
The silver halide grain in the photographic emulsion may have a
regular crystal form such as cubic, octahedral or tetradecahedral,
an irregular crystal form such as spherical or platy, a crystal
defect such as twin, or a composite form of these.
The silver halide grain may be fine grains having a grain size of
about 0.2 .mu.m or less or large-sized grains having a grain size
in terms of a projected area diameter up to about 10 .mu.m, or it
may be either a polydisperse emulsion or a monodisperse emulsion. A
monodisperse emulsion having a dispersion coefficient of 15% or
less, more preferably 10% or less is preferred.
The silver halide photographic emulsion can be prepared according
to the methods described, for example, in Research Disclosure
(hereinafter referred to as RD), No. 17643, pp. 22-23, "I. Emulsion
Preparation and Types" (December, 1978), ibid., No. 18716, p. 648
(November, 1979) and ibid., No. 307105, pp. 863-865 (November,
1989).
Also, tabular grains having an aspect ratio of about 3 or more can
be used in the present invention. The tabular grain can be easily
prepared by the method described in Gutoff, Photographic Science
and Engineerinq, Vol. 14, pp. 248-257 (1970), U.S. Pat. No.
4,434,226 and British Patent 2,112,157.
The crystal structure may be homogeneous, may comprise different
halide compositions between the interior and the exterior or may be
stratified. Silver halides having different compositions may be
conjugated by an epitaxial junction or the silver halide may be
conjugated with a compound other than silver halide, such as silver
rhodanide or lead oxide. A mixture of grains having various crystal
forms may also be used.
The above-described emulsion may be any of a surface latent image
type emulsion mainly forming a latent image on the surface, an
internal latent image type emulsion forming a latent image inside
the grain and an emulsion forming a latent image both on the
surface of and inside the grain, however, the emulsion must be a
negative type emulsion. A core/shell type internal latent image
type emulsion described in JP-A-63-264740, as one of internal
latent image type emulsions, may also be used and methods for
preparing this type emulsion are described in JP-A-59-133542. The
shell thickness of this type emulsion varies depending upon the
development and the like but is preferably from 3 to 40 nm, more
preferably from 5 to 20 nm.
The silver halide emulsion is usually subjected to physical
ripening, chemical ripening and spectral sensitization before use.
The additives used in these steps are described in RD Nos. 17643,
18716 and 307105, and the pertinent portions thereof are summarized
in the table below.
In the photographic material of the present invention, two or more
kinds of emulsions different in at least one property of grain
size, grain size distribution, halogen composition, grain from and
sensitivity can be mixed and used in the same layer.
A silver halide grain with the grain surface being fogged described
in U.S. Pat. No. 4,082,553, a silver halide grain with the inside
of grain being fogged described in U.S. Pat. No. 4,626,498 and
JP-A-59-214852 or silver colloid is preferably used in a
light-sensitive silver halide emulsion layer and/or a substantially
light-insensitive hydrophilic colloidal layer. The silver halide
grain with the inside or surface of grain being fogged indicates a
silver halide grain capable of uniform (namely, non-imagewise)
development irrespective of unexposed and exposed portions of the
photographic material. The silver halide for forming an internal
nucleus of a core/shell type silver halide grain with the inside of
grain being fogged may have a different halide composition. The
silver halide with the inside or surface of grain being fogged may
be any of silver chloride, silver chlorobromide, silver iodobromide
and silver chloroiodobromide. The fogged silver halide grain has an
average grain size of from 0.01 to 0.75 .mu.m, more preferably from
0.05 to 0.6 .mu.m. The grain may have a regular form and a
polydisperse emulsion may be used but a monodisperse emulsion is
preferred.
A light-insensitive fine grained silver halide may also be used.
The light-insensitive fine grained silver halide indicates a silver
halide fine grain which is not exposed at the imagewise exposure
for obtaining a dye image and substantially not developed at the
development and it is preferably not fogged in advance. The finely
grained silver halide has a silver bromide content of from 0 to 100
mole % and, if desired, may contain silver chloride and/or silver
iodide. The silver iodide content is preferably from 0.5 to 10 mole
%. The finely grained silver halide has an average grain size (an
average of circle-corresponding diameters of the projected area) of
preferably from 0.01 to 0.5 .mu.m, more preferably from 0.02 to 0.2
.mu.m.
The finely grained silver halide need neither be optically
sensitized nor spectrally sensitized. However, in advance of
addition to a coating solution, a known stabilizer such as a
triazole-based, azaindene-based, benzothiazolium-based or
marcapto-based compound or a zinc compound is preferably added
thereto. The layer containing this finely grained silver halide
grain may contain silver colloid.
The coated silver amount of a photographic material for
photographing is preferably from 3 to 10 g/mm.sup.2, most
preferably from 4 to 7 g/m.sup.2.
In a photographic material for printing, the silver halide grain
used is preferably a silver chloride, silver chlorobromide or
silver chloroiodobromide grain having a silver chloride content of
95 mole % or more. In particular, in order to expedite the
development time, grains comprising silver chlorobromide or silver
chloride and substantially free of silver iodide are preferably
used. The term "substantially free of silver iodide" as used herein
means that the silver iodide content is 1 mole % or less,
preferably 0.2 mole % or less. On the other hand, for the purpose
of increasing high illumination sensitivity, enhancing spectral
sensitization sensitivity or increasing aging stability of the
photographic material, high silver chloride grains having a silver
iodide content of from 0.01 to 3 mole % may be used on the emulsion
surface in some cases as described in JP-A-3-84545. The halide
composition of the emulsion may be different or the same among
grains but when an emulsion comprising grains having the same
halide composition is used, it is easy to homogenize the properties
of respective grains. Also, with respect to the halide composition
distribution inside of the silver halide emulsion grain, the grain
may have a so-called uniform-type structure where any part of the
silver halide grain has the same composition, a so-called
laminate-type structure where the halide composition is different
between the core inside the silver halide grain and the shell
(single layer or a plurality of layers) surrounding the core or a
structure such that non-layered portions different in the halide
composition are provided inside the grain or on the grain surface
(when provided on the grain surface, the portions different in the
composition are conjugated at edges or corners or on planes), and
these are appropriately selected depending on the use end. For
achieving a high sensitivity, either of the latter two cases is
advantageously used rather than the grain of uniform-type structure
and also preferred in view of pressure stability. When the silver
halide grain has either of the above-described structures, the
boundary between portions different in the halide composition may
be clear, may be unclear resulting from mixed crystals formed due
to difference in the composition or may have sequential structural
change provided positively.
The high silver chloride emulsion preferably has a structure such
that a silver bromide localized phase of layer or non-layer form as
described above is present in the inside and/or on the surface of
silver halide grain. The halide composition of the above-described
localized phase has a silver bromide content preferably of at least
10 mole %, more preferably exceeding 20 mole %. The localized phase
can be present at edges or corners or on planes inside the grain or
on the grain surface and one preferred example is a localized phase
epitaxially grown at a corner of grain.
It is also effective to further increase the silver chloride
content of a silver halide emulsion so as to reduce the
replenishing amount of the development processing solution. In this
case, an emulsion consisting of nearly pure silver chloride as
having a silver chloride content of 98 to 100 mole % is also
preferably used.
The silver halide grain contained in the silver halide emulsion has
an average grain size (a number average of diameters, as a grain
size, of circles each equivalent to the projected area of a grain)
of preferably from 0.1 to 2 .mu.m.
A so-called monodisperse emulsion is preferred having a coefficient
of fluctuation in the grain size distribution (obtained by dividing
the standard deviation of the grain size distribution by the
average grain size) of 20% or less, preferably 15% or less, more
preferably 10% or less. For the purpose of obtaining a wide
latitude, it is also preferred to blend monodisperse emulsions as
described above in the same layer or coat the monodisperse
emulsions in a superposed fashion.
The silver halide grain contained in the photographic emulsion may
have a regular crystal form such as cube, tetradecahedron or
octahedron, an irregular crystal form such as spherical or platy,
or a composite form of these. Also, a mixture of grains having
various crystal forms may be used. In the present invention, grains
having the above-described regular crystal form preferably accounts
for 50% or more, more preferably 70% or more, still more preferably
90% or more. In addition, an emulsion where tabular grains having
an average aspect ratio (diameter in terms of circle/thickness) of
5 or more, preferably 8 or more, exceeds 50% of the total grains in
terms of projected area can also be preferably used.
The localized phase or substrate of the silver halide grain may
contain different kinds of metal ions or their complex ions.
Preferred metals are selected from metal ions or metal complexes
belonging to Group VIII and Group IIb of the Periodic Table, a lead
ion and a thallium ion. In the localized phase, ions selected from
iridium, rhodium or iron or complex ions thereof may be mainly used
in combination and in the substrate, metal ions selected from
osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt,
nickel and iron or complex ions thereof may be mainly used in
combination. The kind and concentration of the metal ion may be
changed between the localized phase and the substrate. These metals
may also be used in a plurality of kinds. In particular, an iron or
iridium compound is preferably present in a silver bromide
localized phase.
The metal ions are incorporated into the localized phase of the
silver halide grain of the present invention and/or other grain
portions (e.g., substrate) by adding a compound which provides the
above-described metal ion to a dispersion medium such as an aqueous
gelatin solution, an aqueous halide solution, an aqueous silver
salt solution or other aqueous solutions during formation of silver
halide grains or by adding thereto silver halide fine grains having
incorporated therein metal ions in advance and then dissolving the
fine grains.
The metal ion used in the present invention can be incorporated
into the emulsion grains before grain formation, during grain
formation or immediately after grain formation. The time may be
changed according to the portion of the grain to which the metal
ions are incorporated.
The silver halide emulsion is usually subjected to chemical
sensitization and spectral sensitization.
The chemical sensitization may be performed by effecting chemical
sensitization using a chalcogen sensitizer (specifically, sulfur
sensitization represented by the addition of a labile sulfur
compound, selenium sensitization using a selenium compound or
tellurium sensitization using a tellurium compound), noble metal
sensitization represented by gold sensitization, or reduction
sensitization, individually or in combination. Preferred examples
of the compound for use in the chemical sensitization include those
described in JP-A-62-215272, from page 18, right lower column to
page 22, right upper column.
The effect provided by the structure of the photographic material
of the present invention is outstanding when a high silver chloride
emulsion subjected to gold sensitization is used. The emulsion used
in the present invention is a so-called surface latent image-type
emulsion where a latent image is mainly formed on the grain
surface.
The silver halide emulsion may contain various compounds or
precursors thereof for the purpose of preventing fog during
preparation, storage or photographic processing of a photographic
material, or for stabilizing the photographic performance. Specific
and preferred examples of these compounds include those described
in JP-A-62-215272, pp. 39-72. The 5-arylamino-1,2,3,4-thiatriazole
compounds (the aryl residue having at least one electron-attractive
group) described in EP 0447647 are also preferably used.
The spectral sensitization is effected so as to impart spectral
sensitivity at a desired light wavelength region to the emulsion of
each layer of a photographic material.
Examples of the spectral sensitization dye used for spectral
sensitization at blue, green and red regions include those
described in F. M. Hamer, Heterocyclic Compounds-Cyanine Dyes and
Related Compounds, John Wiley & Sons, New York, London (1964).
Specific examples of the compound and the spectral sensitization
method include those described in JP-A-62-215272, from page 22,
right upper column to page 38. As the red-sensitive spectral
sensitizing dye particularly for silver halide emulsion grains
having a high silver chloride content, spectral sensitizing dyes
described in JP-A-3-123340 are very preferred in view of stability,
adsorption strength and temperature dependency of exposure.
For efficiently effecting spectral sensitization at the infrared
region, sensitizing dyes described in JP-A-3-15049, from page 12,
left upper column to page 21, left lower column, JP-A-3-20730, from
page 4, left lower column to page 15, left lower column, EP
0420011, from page 4, line 21 to page 6, line 54, EP 0420012, page
4, line 12 to page 10, line 33, EP 0443466 and U.S. Pat. No.
4,975,362 are preferably used.
The time when the spectral sensitizing dye is added to an emulsion
may be any stage hitherto considered useful during preparation of
the emulsion. More specifically, it may be added before grain
formation of silver halide emulsion, during grain formation of
silver halide emulsion, between immediately after grain formation
of silver halide emulsion and prior to entering into a washing
step, before chemical sensitization, during chemical sensitization,
between immediately after chemical sensitization and solidification
under cooling of the emulsion or during preparation of coating
solutions. Most commonly, the dye is added to the emulsion after
completion of chemical sensitization prior to coating but the dye
may be added at the same time with a chemical sensitizer to effect
spectral sensitization and chemical sensitization simultaneously as
described in U.S. Pat. Nos. 3,628,969 and 4,225,666, the dye may be
added in advance of chemical sensitization as described in
JP-A-58-113928, or the dye may be added before precipitation of
silver halide grains is completed to start spectral sensitization.
Further, the spectral sensitizing dye may be added in fractions,
namely, a part may be added in advance of chemical sensitization
and the remaining may be added after chemical sensitization as
described in U.S. Pat. No. 4,225,666, and the addition may be
effected in any time during formation of silver halide grains as
described in U.S. Pat. No. 4,183,756. In particular, the
sensitizing dye is preferably added before water washing or before
chemical sensitization, of the emulsion.
The addition amount of the spectral sensitizing dye changes over a
wide range according to the case but it is preferably in the range
from 0.5.times.10.sup.-6 to 1.0.times.10.sup.-2 mole, more
preferably from 1.0.times.10.sup.-6 to 5.0.times.10.sup.-3 mole,
per mole of silver halide.
In particular, when a sensitizing dye having a spectral
sensitization sensitivity in a region from red to infrared is used
in the present invention, compounds described in JP-A-2-157749,
from page 13, right lower column to page 22, right lower column are
preferably used in combination. By using such a compound,
preservability and processing stability of the photographic
material and supersensitization effect can be peculiarly increased.
Among these, compounds represented by formulae (IV), (V) and (VI)
of JP-A-2-157749 are preferably used in combination. Such a
compound is advantageously used in an amount of from
0.5.times.10.sup.-5 to 5.0.times.10.sup.-2 mole, preferably from
5.0.times.10.sup.-5 to 5.0.times.10.sup.-3 mole, pre mole of the
silver halide, and in a range from 0.1 to 10,000 times, preferably
from 0.5 to 5,000 times, per mole of the sensitizing dye.
The photographic material may contain in a hydrophilic colloidal
layer a dye (particularly, an oxonol dye or a cyanine dye) capable
of decolorization by processing described in EP 0337490A2, pp.
27-76, so as to prevent irradiation or halation or to improve
safety to the safelight.
Some water-soluble dyes may worsen the color separation or safety
to the safelight when used in an increased amount. As the dye which
can be used without causing any deterioration in color separation,
water-soluble dyes described in Japanese Patent Application Nos.
3-310143, 3-310189 and 3-310139 are preferred.
A colored layer capable of decolorization may be used in place of a
water-soluble dye or in combination with a water-soluble dye. The
colored layer capable of decolorization by processings employed may
be put into direct contact with an emulsion layer or may be
provided through an interlayer containing gelatin or a processing
color mixing inhibitor such as hydroquinone. The colored layer is
preferably provided as an underlayer (on the support side) of an
emulsion layer to be colored to the same elementary color as the
color of the colored layer. Colored layers corresponding to every
elementary colors may be individually provided or only a part
thereof may be freely selected and provided. Also, a colored layer
colored so as to correspond to a plurality of elementary color
regions may be provided. With respect to the optical reflection
density of the colored layer, the optical density at a wavelength
having the highest optical density in the wavelength regions used
for exposure (a visible light region of from 400 to 700 nm in the
case of a normal printer exposure and a wavelength of the scan
exposure light source used in the case of scan exposure) is
preferably from 0.2 to 3.0, more preferably from 0.5 to 2.5, still
more preferably from 0.8 to 2.0.
The colored layer can be formed according conventionally known
methods. For example, a method where a dye is incorporated into a
hydrophilic colloid layer in the sate of a solid fine particle
dispersion, such as a dye described in JP-A-2-282244, from page 3,
right upper column to page 8, or a dye described in JP-A-3-7931,
from page 3, right upper column to page 11, left lower column, a
method where an anionic dye is mordanted to a cation polymer, a
method where a dye is adsorbed to fine grains such as silver halide
to fix it in the layer, or a method using colloidal sliver as
described in JP-A-1-239544 may be used. An example of the method
for dispersing a fine dye powder in the solid state include a
method described in JP-A-2-308244, pp. 4-13, where a fine powder
dye substantially water-insoluble at a pH of 6 or less but
substantially water-soluble at a pH of 8 or more is incorporated.
The method for mordanting an anionic dye to a cation polymer is
described, for example, in JP-A-2-84637, pp. 18-26. The preparation
method of colloidal silver as a light absorbent is described in
U.S. Pat. No. 2,688,601 and 3,459,563. Among these methods,
preferred are a method comprising incorporating a fine powder dye
and a method using colloidal silver.
Gelatin is advantageous as the binder or protective colloid which
can be used in the photographic material but other hydrophilic
colloids may be used solely or in combination with gelatin.
Preferred gelatin is a low-calcium gelatin having a calcium content
of 800 ppm or less, more preferably 200 ppm or less. Further, an
antiseptic as described in JP-A-63-271247 is preferably added for
preventing the hydrophilic colloidal layers from proliferation of
various molds or bacteria which cause deterioration of an
image.
At the time when a photographic material for printing is subjected
to printer exposure, a band stop filter described in U.S. Pat. No.
4,880,726 is preferably used. By using this filter, color mixing is
eliminated and color reproduction is outstandingly improved.
An exposed photographic material is subjected to a conventional
color development and for the purpose of rapid processing, it is
bleach-fixed after color development. In particular, when the
above-described high silver chloride emulsion is used, in order to
accelerate desilverization, the bleach-fixing solution has a pH of
preferably about 6.5 or less, more preferably about 6 or less.
The photographic additives which can be used are described in RD
and the pertinent portions are described in the following
table.
______________________________________ Kinds of Additives RD17643
RD18716 RD307105 ______________________________________ 1. Chemical
sensitizer p. 23 p. 648, right p. 866 column 2. Sensitivity
increasing p. 648, right agent column 3. Spectral sensitizer, pp.
23-24 p. 648, right pp. 866-868 supersensitizer column-p. 649,
right column 4. Brightening agent p. 24 p. 647, right p. 868 column
5. Light absorbent, filter pp. 25-26 p. 649, right p. 873 dye, UV
absorbent column-p. 650, left column 6. Binder p. 26 p. 651, left
pp. 873-874 column 7. Plasticizer, lubricant p. 27 p. 650, right p.
876 column 8. Coating aid, surface pp. 26-27 p. 650, right pp.
875-876 active agent column 9. Antistatic agent p. 27 p. 650, right
pp. 876-877 column 10. Matting agent pp. 878-879
______________________________________
Various dye-forming couplers may be used in the photographic
material but the following couplers are particularly preferred.
Yellow Coupler
Couplers represented by formulae (I) and (II) of EP 502424A;
couplers represented by formulae (1) and (2) of EP 513496A
(particularly Coupler Y-28 at page 18); couplers represented by
formula (I) in claim 1 of Japanese Patent Application No. 4-134523;
couplers represented by formula (I) in column 1, lines 45 to 55 of
U.S. Pat. No. 5,066,576; couplers represented by formula (I) in
paragraph [0008] of JP-A-4-274425; couplers described in claim 1 at
page 40 of EP 498381A1 (particularly Coupler D-35 at page 18);
couplers represented by formula (Y) at page 4 of EP 447969A1
(particularly Couplers Y-1 (p. 17) and Y-54 (p. 41)); couplers
represented by formulae (II) to (IV) in column 7, lines 36 to 58 of
U.S. Pat. No. 4,476,219 (particularly Couplers II-17 and II-19
(col. 17) and II-24 (col. 19)); and acylacetanilide-based couplers,
in particular, pivaloyl-acetanilide-based couplers having a halogen
atom or an alkoxy group at the orth-position of the anilide ring,
acylacet-anilide-based couplers with the acyl group being a
cyclo-alkanecarbonyl group substituted at the 1-position described
in EP 0447969A, JP-A-5-107701 and JP-A-5-113642, and
malondianilide-based couplers described in EP 0482552A and EP
0524540A.
Magenta Couplers
Couplers L-57 (p. 11, right lower column), L-68 (p. 12, right lower
column) and L-77 (p. 13, right lower column) of JP-A-3-39737;
Couplers [A-4]-63 (p. 134), [A-4]-73 and [A-4]-75 (p. 139) of EP
456257; Couplers M-4 and M-6 (p. 26) and M-7 (p. 27) of EP 486965;
Coupler M-45 in paragraph [0024] of Japanese Patent Application No.
4-234120; Coupler M-1 in paragraph [0036] of Japanese Patent
Application No. 4-36917; Coupler M-22 in paragraph [0237] of
JP-A-4-362631; 5-pyrazolone-based magenta couplers such as
arylthio-releasing 5-pyrazolone-based magenta couplers described in
International Applications W092/18901, W092/18902 and W092/18903;
and pyrazoloazole type couplers such as pyrazoloazole couplers
containing a sulfonamido group in the molecule described in
JP-A-61-65246, pyrazoloazole couplers having an
alkoxyphenylsulfonamido ballast group described in JP-A-61-147254
and pyrazoloazole couplers having an alkoxy group or an aryloxy
group at the 6-position described in European Patents 226849A and
294785A.
Cyan Couplers
Couplers CX-1, CX-3, CX-4, CX-5, CX-11, CX-12, CX-14 and CX-15 (pp.
14-16) of JP-A-4-204843; Couplers C-7 and 10 (p. 35), C-34 and C-35
(p. 37), (I-1) and (I-17) (pp. 42-43) of JP-A-4-43345; and couplers
represented by formulae (Ia) and (Ib) of claim 1 of Japanese Patent
Application No. 4-236333.
Polymer Coupler
Couplers P-1 and P-5 (p. 11) of JP-A-2-44345.
Phenol-based couplers and naphthol-based couplers,
diphenylimidazole-based cyan couplers described in JP-A-2-33144,
3-hydroxypyridine-based cyan couplers described in EP 0333185A2,
cyclic active methylene-based cyan couplers described in
JP-A-64-32260, pyrrolopyrazole-type cyan couplers described in EP
0456226A1, pyrroloimidazole-type cyan couplers described in EP
0484909 and pyrrolotriazole-type cyan couplers described in EP
0488248 and EP 0491197A1.
As the coupler which provides a dye having an appropriate
diffusibility, those described in U.S. Pat. No. 4,366,237, British
Patent 2,125,570, European Patent 96873B, and West German Patent
(OLS) No. 3,234,533 are preferred.
Preferred examples of the coupler which corrects unnecessary
absorption of the coloring dye include yellow colored cyan couplers
represented by formulae (CI), (CII), (CIII) and (CIV) at page 5 of
EP 456257A1 (particularly Coupler YC-86 at page 84), Yellow Colored
Magenta Couplers ExM-7 (p. 202), EX-1 (p. 249) and EX-7 (p. 251) of
the European patent cited above, Magenta Colored Cyan Couplers CC-9
(col. 8) and CC-13 (col. 10) of U.S. Pat. No. 4,883,069, Coupler
(2) (col. 8) of U.S. Pat. No. 4,837,136 and colorless masking
couplers represented by formula (A) in claim 1 of W092/11575
(particularly compounds illustrated at pp. 36-45).
A compound (including a coupler) which releases a photographically
useful residue on reaction with an oxidation product of the color
developing agent includes the following: a development
inhibitor-releasing compound such as compounds represented by
formulae (I), (II), (III) and (IV) at page 11 of EP 378236A1
(particularly, T-101 (p. 30), T-104 (p. 31), T-113 (p. 36), T-131
(p. 45), T-144 (p. 51) and T-158 (p. 58)), compounds represented by
formula (I) at page 7 of EP 436938A2 (particularly, D-49 (p. 51)),
compounds represented by formula (1) of Japanese Patent Application
No. 4-134523 (particularly Compound (23) in para. 0027) and
compounds represented by formulae (I), (II) and (III) at pages 5 to
6 of EP 440195A2 (particularly Compound I-(1) at p. 29); a
bleaching accelerator-releasing compound such as compounds
represented by formulae (I) and (I') at page 5 of EP 310125A2
(particularly Compounds (60) and (61) at p. 61) and compounds
represented by formula (I) in claim 1 of Japanese Patent
Application No. 4-325564 (particularly Compound (7) in para. 0022);
a ligand-releasing compound such as compounds represented by LIG-X
in claim 1 of U.S. Pat. No. 4,555,478 (particularly compounds
described in col. 12, lines 21-41); a leuco dye-releasing compound
such as Compounds 1 to 6 in columns 3 to 8 of U.S. Pat. No.
4,749,641; a fluorescent dyereleasing compound such as compounds
represented by COUP-DYE in claim 1 of U.S. Pat. No. 4,774,181
(particularly Compounds 1 to 11 in cols. 7-10); a development
accelerator or fogging agent-releasing compound such as compounds
represented by formulae (1), (2) and (3) in column 3 of U.S. Pat.
No. 4,656,123 (particularly Compound (I-22) in col. 25) and ExZK-2
at page 75, lines 36 to 38 of EP 450637A2; and a compound releasing
a group which becomes a dye first when it is released such as
compounds represented by formula (I) in claim 1 of U.S. Pat. No.
4,857,447 (particularly Compounds Y-1 to Y-19 in cols. 25-36).
Preferred examples of additives other than couplers include the
following: a dispersion medium of an oil-soluble organic compound
such as Compounds P-3, P-5, P-16, P-19, P-25, P-30, P-42, P-49,
P-54, P-55, P-66, P-81, P-85, P-86 and P-93 (pp. 140-144) of
JP-A-62-215272; a latex for impregnation of an oil-soluble organic
compound such as latices described in U.S. Pat. No. 4,199,363; an
oxidation product scavenger of a developing agent such as compounds
represented by formula (I) in column 2, lines 54 to 62 of U.S. Pat.
No. 4,978,606 (particularly Compounds I-(1), I-(2), I-(6) and
I-(12) (cols. 4-5)) and compounds represented by the formula in
column 2, lines 5 to 10 of U.S. Pat. No. 4,923,787 (particularly
Compound 1 (col. 3)); a stain inhibitor such as compounds
represented by formulae (I) to (III) at page 4, lines 30 to 33 of
EP 298321A (particularly Compounds I-47, I-72, II-1 and III-27 (pp.
24-48)); a discoloration inhibitor such as Compounds A-6, A-7,
A-20, A-21, A-23, A-24, A-25, A-26, A-30, A-37, A-40, A-42, A-48,
A-63, A-90, A-92, A-94 and A-164 (pp. 69-118) of EP 298321A,
compounds II-1 to III-23 in columns 25 to 38 of U.S. Pat. No.
5,122,444 (particularly Compound III-10), Compounds I-1 to III-4 at
pages 8 to 12 of EP 471347A (particularly Compound II-2) and
Compounds A-1 to A-48 in columns 32 to 40 of U.S. Pat. No.
5,139,931 (particularly Compounds A-39 and A-42); a material able
to reduce the use amount of a color reinforcing agent or a color
mixing inhibitor such as Compounds I-1 to II-15 at pages 5 to 24 of
EP 411324A (particularly Compound I-46); a formalin scavenger such
as Compounds SCV-1 to SCV-28 at pages 24 to 29 of EP 477932A
(particularly Compound SCV-8); a hardening agent such as Compounds
H-1, H-4, H-6, H-8 and H-14 at page 17 of JP-A-1-214845, Compounds
(H-1) to (H-54) represented by formulae (VII) to (XII) in columns
13 to 23 of U.S. Pat. No. 4,618,573, Compounds (H-1) to (H-76)
represented by formula (6) at page 8, right lower column of
JP-A-2-214852 (particularly Compound H-14) and compounds in claim 1
of U.S. Pat. No. 3,325,287; a development inhibitor precursor such
as Compounds P-24, P-37 and P-39 (pp. 6-7) of JP-A-62-168139;
compounds in claim 1 of U.S. Pat. No. 5,019,492 (particularly
Compounds 28 and 29 in col. 7); an antiseptic and an antimold such
as Compounds I-1 to III-43 in columns 3 to 15 of U.S. Pat. No.
4,923,790 (particularly Compounds II-1, II-9, II-10, II-18 and
III-25); a stabilizer and an antifoggant such as Compounds I-1 to
(14) in columns 6 to 16 of U.S. Pat. No. 4,923,793 (particularly
Compounds I-1, I-60, (20) and (13)) and Compounds 1 to 65 in
columns 25 to 32 of U.S. Pat. No. 4,952,483 (particularly Compound
36); a chemical sensitizer such as triphenylphosphine, selenide and
Compound 50 of JP-A-5-40324; a dye such as Compounds a-1 to b-20 at
pages 15 to 18 (particularly Compounds a-1, a-12, a-18, a-27, a-35,
a-36, b-5) and Compounds V-1 to V-23 at pages 27 to 29
(particularly Compound V-1) of JP-A-3-156450, Compounds F-I-1 to
F-II-43 at pages 33 to 55 (particularly Compounds F-I-11 and
F-II-8) of EP 445627A, Compounds III-1 to III-36 at pages 17 to 28
of EP 457153A (particularly Compounds III-1 and III-3), fine
crystal dispersions of Dye-1 to Dye-124 at pages 8 to 26 of WO
88/04794, Compounds 1 to 22 at pages 6 to 11 of EP 319999A
(particularly Compound 1), Compounds D-1 to D-87 (pp. 3-28)
represented by formulae (1) to (3) of EP 519306A, Compounds 1 to 22
(cols. 3-10) represented by formula (I) of U.S. Pat. No. 4,268,622
and Compounds (1) to (31) (cols. 2-9) represented by formula (I) of
U.S. Pat. No. 4,923,788; a UV absorbent such as Compounds (18b) to
(18r) and 101 to 427 (pp. 6-9) represented by formula (1) of
JP-A-46-3335, Compounds (3) to (66) (pp. 10-44) represented by
formula (I) and Compounds HBT-1 to HBT-10 (p. 14) represented by
formula (III) of EP 520938A and Compounds (1) to (31) (cols. 2-9)
represented by formula (1) of EP 521823A.
The support for use in a photographic material for printing may be
any support as long as it is a support on which photographic
emulsion layers can be coated, such as glass, paper or plastic
film, and the most preferred is a reflection-type support.
The "reflection-type support" as used in the present invention
means a support able to render a dye image formed on the silver
halide emulsion layer sharp owing to the increased reflectivity and
such a reflection-type support includes those obtained by covering
the support with a hydrophobic resin having dispersed therein and
containing a light-reflective substance such as titanium oxide,
zinc oxide, calcium carbonate or calcium sulfate, or a hydrophobic
resin having dispersed therein and containing a light-reflective
substance may be used by itself as the support. Examples thereof
include a polyethylene-coated paper, polyethylene
terephthalate-coated paper, polypropylene-based synthetic paper, a
transparent support having provided thereon a reflection layer or
comprising a reflective substance in combination such as a glass
plate, a polyester film (e.g., polyethylene terephthalate,
cellulose triacetate, cellulose nitrate), a polyamide film, a
polycarbonate film, a polystyrene film and a vinyl chloride resin.
The reflection-type support used in the present invention is
preferably a paper support of which both surfaces are coated with
waterproof resin layers, with at least one of waterproof resin
layers containing white pigment fine particles.
The waterproof resin for the reflection support has a water
absorptivity of 0.5 wt %, preferably 0.1 wt % or less and examples
thereof include polyethylene, polypropylene, polyolefin such as a
polyethylene-based polymer, vinyl polymer or a copolymer thereof
(e.g., polystyrene, polyacrylate or a copolymer thereof) and
polyester (e.g., polyethylene terephthalate, polyethylene
isophthalate) or a copolymer thereof. Among these, preferred are
polyethylene and polyester.
The polyethylene may be a high density polyethylene, a low density
polyethylene, a linear low density polyethylene or a blend of these
polyethylenes. The polyethylene before processing has a melt flow
rate (hereinafter referred to as MFR), determined according to JIS
K 7210, Condition 4 in Table 1, of preferably from 1.2 g/10 min. to
12 g/10 min. The MFR of the polyolefin resin before processing
indicates the MFR of the resin before a bluing agent and a white
pigment are kneaded thereinto.
The mixing ratio by weight of the above-described waterproof resin
to the white pigment is from 98/2 to 30/70 (waterproof resin/white
pigment), preferably from 95/5 to 50/50, more preferably from 90/10
to 60/40. If the amount of the white pigment is less than 2 wt %,
the pigment cannot contribute to the whiteness sufficiently,
whereas if it exceeds 70 wt %, the surface smoothness when formed
into a photographic support is unsatisfactory to fail in achieving
a photographic support having excellent gloss.
The waterproof resin layer is preferably coated on a substrate in a
thickness of from 2 to 200 .mu.m, more preferably from 5 to 80
.mu.m. If the thickness exceeds 200 .mu.m, the brittleness of resin
is intensified to cause problems in physical properties such as
cracking, whereas if it is less than 2 .mu.m, not only the
waterproof property as the original object of its coating is
impaired but also the whiteness and the surface smoothness both
cannot be satisfied and in addition, the resin is too much soft and
disadvantageous in view of physical properties.
The resin or the resin composition coated on a substrate surface
different from the side where light-sensitive layers are coated has
a thickness of preferably from 5 to 100 .mu.m, more preferably from
10 to 50 .mu.m. If the thickness exceeds this range, the
brittleness of resin is intensified to cause problems in physical
properties such as cracking, whereas if it is less than this range,
not only the waterproof property as the original object of its
coating is impaired but also the resin is too much soft and
disadvantageous in view of physical properties.
In some cases, in view of the cost and production aptitude of the
support, the waterproof resin-coated layer of the reflection
support on side where light-sensitive layers are coated preferably
consists of two or more waterproof resin-coated layers different in
the white pigment content. In this case, among the waterproof
resin-coated layers different in the white pigment content, the
waterproof resin-coated layer nearest to the substrate preferably
has a white pigment content lower than the white pigment content of
at least one waterproof resin-coated layer provided upper than the
layer above. In still more preferred embodiment, the reflection
support comprises waterproof resin-coated layers different in the
white pigment content, wherein the waterproof resin-coated layer
nearest to the light-sensitive layer has a highest white pigment
content, or the reflection support comprises at least three
waterproof resin-coated layers, wherein in the multilayer
waterproof resin layer, any interlayer other than the waterproof
resin-coated layer nearest to the light-sensitive layer and the
waterproof resin-coated layer nearest to the substrate has a
highest white pigment content.
The white pigment content in each layer of the multilayer
waterproof resin layer is from 0 to 70 wt %, preferably from 0 to
50 wt %, more preferably from 0 to 40 wt %. In the multilayer
waterproof resin layer, the layer having the highest white pigment
content has a white pigment content of from 9 to 70 wt %,
preferably from 15 to 50 wt %, more preferably from 20 to 40 wt %.
If the white pigment content of this layer is less than 9 wt %, the
image is low in sharpness, whereas if it exceeds 70 wt %, the film
after melt-extrusion undergoes cracking.
Each layer of the multilayer waterproof resin layer preferably has
a thickness of from 0.5 to 50 .mu.m. For example, in the case of a
multilayer waterproof resin layer comprising two layers, each layer
preferably has a thickness of from 0.5 to 50 .mu.m and the total
thickness of two layers preferably falls in the above-described
range (from 2 to 200 .mu.m). In the case of a three-layer
structure, it is preferred that the uppermost layer has a thickness
of from 0.5 to 10 .mu.m, the intermediate layer has a thickness of
from 5 to 50 .mu.m and the lowermost layer (a layer nearest to the
substrate) has a thickness of from 0.5 to 10 .mu.m. If the
thickness of the uppermost and lowermost layers is less than 0.5
.mu.m, die lip streaks are readily generated due to action of the
white pigment highly charged in the intermediate layer. On the
other hand, the thickness of the uppermost and lowermost layers, in
particular, of the uppermost layer, is larger than 10 .mu.m, the
sharpness is reduced.
The white pigment fine particles are preferably dispersed uniformly
in the reflection layer without causing aggregate of particles and
the size of distribution can be obtained by determining the
occupied area ratio (%) (Ri) of fine particles projected per the
unit area. The coefficient of fluctuation in the occupied area
ratio (%) can be obtained by the ratio s/R where R is an average of
Ri and s is the standard deviation of Ri. In the present invention,
the coefficient of fluctuation in the occupied area ratio (%) of
pigment fine particles is preferably 0.15 or less, more preferably
0.12 or less, still more preferably 0.08 or less.
A support having a surface of a second-class diffuse reflection may
be used. The second-class diffuse reflection means the diffuse
reflection obtained when the specular surface is made uneven to
have finely divided specular faces directed toward different
directions and the directions of finely divided surface (specular
faces) are decentralized. The unevenness on the surface of
second-class diffuse reflection is preferably provided such that
the threedimensional average height to the center plane is from 0.1
to 2 .mu.m, preferably from 0.1 to 1.2 .mu.m and the frequency of
unevenness having a height of 0.1 .mu.m or more on the surface is
preferably from 0.1 to 2,000 cycles/mm, more preferably from 50 to
600 cycles/mm. JP-A-2-239244 describes such a support in
detail.
Examples of the support suitable for a photographic material are
described in RD No. 17643, page 28, RD No. 18716, from page 647,
right column to page 648, left column and RD No. 307105, page
879.
In case of a photographic material for photographing, the total
thickness of entire hydrophilic colloid layers on the side having
emulsion layers is preferably 23 .mu.m or less, more preferably 20
.mu.m or less, still more preferably from 13 to 17 .mu.m. The layer
swelling speed T.sub.1/2 is preferably from 5 to 15 seconds.
T.sub.1/2 is defined as the time required to reach a half of the
saturated film thickness which corresponds to 90% of the maximum
swelled film thickness achieved in the processing with a color
developer at 30.degree. C. for 3 minutes and 15 seconds. The
swelling speed T.sub.1/2 can be controlled by adding a hardening
agent to gelatin as a binder or by changing the aging condition
after coating. Also, the swelling ratio is preferably from 150 to
350%. The swelling ratio can be calculated by the equation:
(maximum swelled film thickness--film thickness)/film thickness,
from the maximum swelled film thickness obtained under conditions
described above.
The photographic material may comprise hydrophilic colloid layers
(referred to as a back layer) having a total dry thickness of from
2 to 20 .mu.m provided on the side opposite to the emulsion layer
side. The back layer preferably contains a light absorbent, a
filter dye, an ultraviolet absorbent, an antistatic agent, a
hardening agent, a binder, a plasticizer, a lubricant, a coating
aid or a surface active agent. The back layer preferably has a
selling ratio of from 150 to 500%.
According to the present invention, a rapid processing can be
conducted and also the dye image obtained can be well balanced in
colors.
By incorporating a color developing agent into the developer, the
color balance is further improved.
The present invention is particularly effective when the color
photographic material having light sensitivity comprises silver
iodobromide emulsions, when the compound represented by formula (D)
is used as a solid dispersion and when the color developer is
replenished at a low rate.
EXAMPLE 1
A multi-layer color photographic material as Sample 101 was
prepared by coating layers each having the following composition in
a superposed fashion on a cellulose triacetate film support having
a subbing layer.
Composition of light-sensitive layer
Main materials used in each layer are classified as follows:
ExC: cyan coupler
ExM: magenta coupler
ExY: yellow coupler
ExS: sensitizing dye
UV: ultraviolet absorbent
HBS: high-boiling point organic solvent
H: gelatin hardening agent
Numerals corresponding to respective ingredients show coating
amounts expressed by the unit g/m.sup.2 and in case of silver
halide, they show coating amounts in terms of silver. With respect
to sensitizing dyes, the coating amount is shown by the unit "mole"
per mole of silver halide in the same layer.
(Sample 101)
______________________________________ First Layer (antihalation
layer) Black colloidal silver as silver 0.18 Gelatin 1.40 ExM-1
0.11 ExF-1 3.4 .times. 10.sup.-3 HBS 0.16 Second Layer (interlayer)
ExC-2 0.030 UV-1 0.020 UV-2 0.020 UV-3 0.060 HBS-1 0.05 HBS-2 0.020
Polyethylacrylate latex 0.080 Gelatin 0.90 Third Layer (low
sensitive red-sensitive emulsion layer) Emulsion A as silver 0.23
Emulsion B as silver 0.23 ExS-1 5.0 .times. 10.sup.-4 ExS-2 1.8
.times. 10.sup.-5 ExS-3 5.0 .times. 10.sup.-4 ExC-1 0.045 ExC-3
0.030 ExC-4 0.12 ExC-5 3.0 .times. 10.sup.-3 ExC-7 1.0 .times.
10.sup.-3 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.08 Gelatin 0.08 Fourth
Layer (medium sensitive red-sensitive emulsion layer) Emulsion C as
silver 0.70 ExS-1 3.4 .times. 10.sup.-4 ExS-2 1.2 .times. 10.sup.-5
ExS-3 4.0 .times. 10.sup.-4 ExC-1 0.15 ExC-2 0.060 ExC-4 0.050
ExC-5 0.010 ExC-8 0.010 Cpd-2 0.023 HBS-1 0.08 Gelatin 0.55 Fifth
Layer (high sensitive red-sensitive emulsion layer) Emulsion D as
silver 1.62 ExS-1 2.4 .times. 10.sup.-4 ExS-2 1.0 .times. 10.sup.-5
ExS-3 3.0 .times. 10.sup.-4 ExC-1 0.10 EXC-3 0.050 ExC-5 2.0
.times. 10.sup.-3 ExC-6 0.010 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.20
HBS-2 0.10 Gelatin 1.30 Sixth Layer (interlayer) Cpd-1 0.090 HBS-1
0.05 Polyethylacrylate latex 0.15 Gelatin 1.10 Seventh Layer (low
sensitive green-sensitive emulsion layer) Emulsion E as silver 0.24
Emulsion F as silver 0.24 ExS-4 4.0 .times. 10.sup.-5 ExS-5 1.8
.times. 10.sup.-4 ExS-6 6.5 .times. 10.sup.-4 ExM-1 5.0 .times.
10.sup.-3 ExM-2 0.28 ExM-3 0.086 ExM-4 0.030 ExY-1 0.015 HBS-1 0.30
HBS-3 0.010 Gelatin 0.85 Eighth Layer (medium sensitive
green-sensitive emulsion layer) Emulsion G as silver 0.94 ExS-4 2.0
.times. 10.sup.-5 ExS-5 1.4 .times. 10.sup.-4 ExS-6 5.4 .times.
10.sup.-4 ExM-2 0.14 ExM-3 0.045 ExM-5 0.020 ExY-1 7.0 .times.
10.sup.-3 ExY-4 2.0 .times. 10.sup.-3 ExY-5 0.020 HBS-1 0.16 HBS-3
8.0 .times. 10.sup.-3 Gelatin 0.80 Ninth Layer (high sensitive
green-sensitive emulsion layer) Emulsion H as silver 1.29 ExS-4 3.7
.times. 10.sup.-5 ExS-5 8.1 .times. 10.sup.-5 ExS-6 3.2 .times.
10.sup.-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.050 ExM-5 0.020 ExY-4 5.0
.times. 10.sup.-3 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08
Polyethylacrylate latex 0.26 Gelatin 1.45 Tenth Layer (yellow
filter layer) Yellow colloidal silver as silver 7.5 .times.
10.sup.-3 Cpd-1 0.13 Cpd-4 7.5 .times. 10.sup.-3 HBS-1 0.60 Gelatin
0.60 Eleventh Layer (low sensitive blue-sensitive emulsion layer)
Emulsion I as silver 0.25 Emulsion J as silver 0.25 Emulsion K as
silver 0.10 ExS-7 8.0 .times. 10.sup.-4 ExC-7 0.010 ExY-1 5.0
.times. 10.sup.-3 ExY-2 0.40 ExY-3 0.45 ExY-4 6.0 .times. 10.sup.-3
ExY-6 0.10 HBS-1 0.30 Gelatin 1.65 Twelfth Layer (high sensitive
blue-sensitive emulsion layer) Emulsion L as silver 1.30 ExS-7 3.0
.times. 10.sup.-4 ExY-2 0.15 ExY-3 0.06 ExY-4 5.0 .times. 10.sup.-3
Cpd-2 0.10 HBS-1 0.070 Gelatin 1.20 Thirteenth Layer (first
protective layer) UV-2 0.10 UV-3 0.12 UV-4 0.30 HBS-1 0.10 Gelatin
2.50 Fourteenth Layer (second protective layer) Emulsion M as
silver 0.10 H-1 0.37 B-1 (diameter: 1.7 .mu.m) 5.0 .times.
10.sup.-2 B-2 (diameter: 1.7 .mu.m) 0.15 B-3 0.05 S-1 0.20 Gelatin
0.70 ______________________________________
Further, in order to provide good preservability, processability,
pressure resistance, antimold/fungicidal property, antistatic
property and coatability, W-1, W-2, W-3, B-4, B-5, B-6, F-1, F-2,
F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14,
F-15, F-16, F-17, iron salt, lead slat, gold salt, platinum salt,
iridium salt, palladium salt or rhodium salt was appropriately
added to each layer.
Cpd-4 was dispersed as a solid state according to the method
described in International Patent W088/4794.
TABLE 1
__________________________________________________________________________
Coefficient of Fluctuation in Sphere- Average Iodide corresponding
Coefficient of AgI Distribution Average Grain Fluctuation in
Diameter/ Content in Grains Size Grain Size Thickness Emulsion
Grain Form (halogen structure) (%) (%) (.mu.m) (%) Ratio
__________________________________________________________________________
A circular, tabular (uniform structure) 0 -- 0.45 15 5.5 B cubic
(shell high iodide double 1.0 -- 0.20 8 1 structure) C
tetradecahedral (medium shell high iodide 4.5 25 0.85 18 1 triple
structure) D hexagonal, tabular (external high iodide 2.0 16 1.10
17 7.5 structure) E circular, tabular (external high iodide 1.0 --
0.45 15 3.0 structure) F octahedral (core high iodide double 6.0 22
0.25 8 1 structure) G tetradecahedral (medium shell high iodide 4.5
19 0.85 19 1 triple structure) H hexagonal, tabular (external high
iodide 3.5 16 1.10 16 6.8 structure) I circular, tabular (center
high iodide 2.0 15 0.45 15 6.0 structure) J cubic (uniform
structure) 1.0 10 0.30 8 1 K tetradecahedral (core high iodide
double 18.0 8 0.80 18 1 structure) L hexagonal, tabular (medium
shell high 12.0 12 1.35 22 12.0 iodide triple structure) M
light-insensitive fine grain (uniform 1.0 -- 0.04 15 1 structure)
__________________________________________________________________________
In Table 1: (1) Emulsions I to L were subjected to reduction
sensitization at the grain preparation using thiourea dioxide and
thiosulfonic acid according to the example of JPA-2-191938; (2)
Emulsions A to I were subjected to gold sensitization, sulfur
sensitization and selenium sensitization in the presence of the
spectral sensitizing dyes described in each lightsensitive layer
and sodium thiocyanate according to the example of JPA-3-237450;
(3) in the preparation of tabular grains, low molecular weight
gelatin wa used according to the example of JPA-1-158426; and (4)
in tabular grains, dislocation lines were observed through a
highpressure electron microscope as described in JPA-3-237450.
Couplers and additives in each layer were dispersed in a gelatin
solution according to the method shown in Table 2. The addition
method in each layer is shown in Table 3.
TABLE 2 ______________________________________ Dispersion Method
Method ______________________________________ A A uniform aqueous
solution comprising couplers, high-boiling point organic solvent,
surface active agent, NaOH, n-propanol and other additives were
neutralized, deposited and dispersed. B A uniform n-propanol
solution comprising couplers, high-boiling point organic solvents
and other additives were added to an aqueous solution of a surface
active agent, deposited and dispersed. C A solution comprising
couplers, high-boiling point organic solvents, surface active
agents, low-boiling point organic solvent and other additives and
an aqueous solution of gelatin and a surface active agent were
mixed, stirred and emulsion-dispersed and then the low- boiling
organic solvents were removed by evaporation. D The same as Method
C but additionally, the organic solvent was removed by water
washing or ultrafiltration after dispersion.
______________________________________
TABLE 3 ______________________________________ Dispersion Average
Dispersed Grain Size Layer Method (nm)
______________________________________ 3rd Layer C 133 4th Layer C
130 5th Layer D 40 7th Layer C 135 8th Layer C 60 9th Layer A 40
11th Layer C 125 12th Layer B 80
______________________________________ ##STR6##
Samples 102 to 109 were prepared thoroughly in the same manner as
Sample 101 except that the compound of formula (D) of the present
invention was dissolved in an oil for dispersion (HBS) used in the
layer where the compound was added, emulsion-dispersed and then
added. These samples were processed by Processings A and B
described later after exposure. With respect to each of the yellow,
magenta and cyan color images obtained, the density D.sub.2 at an
exposure amount E satisfying logE=logE.sub.0 +2 where E.sub.0 is an
exposure to give the density D.sub.0 of (fog density+0.2) was
measured and from these values, the gradation defined as a value of
(D.sub.2 -D.sub.0)/2 was determined and the results are shown in
FIG. 4.
TABLE 4
__________________________________________________________________________
Layer Addition Sample Compound where (D) Amount of (D) Gradation
(D.sub.2 -D.sub.0)/2 No. No. (D) was added (mmole/m.sup.2)
Processing Yellow Magenta Cyan Remarks
__________________________________________________________________________
1-1 101 None -- -- A 1.14 1.12 1.08 Comparison 1-2 102 (3) 7th
layer 1.0 A 1.27 1.34 1.17 Comparison 1-3 103 (5) 11th layer 1.0 A
1.30 1.25 1.13 Comparison 1-4 104 (13) 10th layer 1.0 A 1.31 1.27
1.14 Comparison 1-5 105 (17) 6th layer 1.0 A 1.26 1.32 1.18
Comparison 1-6 106 (3) 3rd layer 1.0 A 1.28 1.29 1.30 Invention 1-7
107 (5) 2nd layer 1.0 A 1.29 1.30 1.31 Invention 1-8 108 (13) 2nd
layer 1.0 A 1.27 1.29 1.29 Invention 1-9 109 (17) 3rd layer 1.0 A
1.28 1.29 1.30 Invention 1-10 101 none -- -- B 0 0 0 Comparison
1-11 102 (3) 7th layer 1.5 B 0.44 0.52 0.31 Comparison 1-12 103 (5)
11th layer 1.5 B 0.50 0.42 0.28 Comparison 1-13 104 (13) 10th layer
1.5 B 0.51 0.43 0.30 Comparison 1-14 105 (17) 6th layer 1.5 B 0.39
0.51 0.34 Comparison 1-15 106 (3) 3rd layer 1.5 B 0.39 0.40 0.42
Invention 1-16 107 (5) 2nd layer 1.5 B 0.41 0.43 0.45 Invention
1-17 108 (13) 2nd layer 1.5 B 0.39 0.42 0.42 Invention 1-18 109
(17) 3rd layer 1.5 B 0.40 0.42 0.44 Invention
__________________________________________________________________________
As is clear from Table 4, 1-6 to 1-9 and 1-15 to 1-18 of the
Invention showed good color balance in three colors of yellow,
magenta and cyan as compared with 1-1 to 1-5 and 1-10 to 1-14 for
comparison. Also, the color balance was good in Processing A where
the color developer contained Color Developing Agent P-5 as
compared with that in Processing B where the color developer did
not contain Color Developing Agent P-5.
EXAMPLE 2
Example 1 was repeated except for changing the processing methods
to Processings C and D and the results obtained are shown in Table
5.
TABLE 5
__________________________________________________________________________
Layer Addition Sample Compound where (D) Amount of (D) Gradation
(D.sub.2 -D.sub.0)/2 No. No. (D) was added (mmole/m.sup.2)
Processing Yellow Magenta Cyan Remarks
__________________________________________________________________________
2-1 101 None -- -- C 1.12 1.14 0.78 Comparison 2-2 102 (3) 7th
layer 1.0 C 1.21 1.31 0.87 Comparison 2-3 103 (5) 11th layer 1.0 C
1.32 1.21 0.82 Comparison 2-4 104 (13) 10th layer 1.0 C 1.30 1.27
0.83 Comparison 2-5 105 (17) 6th layer 1.0 C 1.20 1.28 0.91
Comparison 2-6 106 (3) 3rd layer 1.0 C 1.17 1.19 1.15 Invention 2-7
107 (5) 2nd layer 1.0 C 1.18 1.19 1.21 Invention 2-8 108 (13) 2nd
layer 1.0 C 1.16 1.20 1.18 Invention 2-9 109 (17) 3rd layer 1.0 C
1.19 1.19 1.17 Invention 2-10 101 none -- -- D 0 0 0 Comparison
2-11 102 (3) 7th layer 1.5 D 0.37 0.41 0.25 Comparison 2-12 103 (5)
11th layer 1.5 D 0.41 0.31 0.21 Comparison 2-13 104 (13) 10th layer
1.5 D 0.39 0.37 0.23 Comparison 2-14 105 (17) 6th layer 1.5 D 0.27
0.40 0.31 Comparison 2-15 106 (3) 3rd layer 1.5 D 0.31 0.34 0.35
Invention 2-16 107 (5) 2nd layer 1.5 D 0.35 0.36 0.38 Invention
2-17 108 (13) 2nd layer 1.5 D 0.32 0.34 0.36 Invention 2-18 109
(17) 3rd layer 1.5 D 0.34 0.35 0.37 Invention
__________________________________________________________________________
As is clear from Table 5, in a rapid processing, 2-6 to 2-9 and
2-15 to 2-18 of the Invention showed good color balance in three
colors of yellow, magenta and cyan as compared with 2-1 to 2-5 and
2-10 to 2-14 for comparison. The effect was more outstanding in a
rapid processing. Also, the color balance was good in Processing C
where the color developer contained Color Developing Agent P-5 as
compared with that in Processing D where the color developer did
not contain Color Developing Agent P-5.
EXAMPLE 3
Example 2 was repeated except for changing the processing methods
to Processings E and F and although development was conducted in
the same way as in Example 2, almost the same results as in Example
2 were obtained.
EXAMPLE 4
The compound of formula (D) was subjected to ball milling according
to the method described below. 110 ml of water and 200 ml of a 6.7%
aqueous solution of Triton X-200 surface active agent (TX-200) were
poured in a 500 ml-volume ball mill. 5 g of the compound of formula
(D) was added to the solution. After adding thereto 100 ml of beads
(diameter: 2 mm) of zirconium oxide (ZnO), the contents were ground
for 4 days. Thereafter, 160 g of 12.5% gelatin was added thereto.
After defoaming, ZrO beads were removed by filtration. Samples 111
to 113 were prepared thoroughly in the same manner as in Example 1
except that the dispersion of the compound of formula (D) obtained
above was added to layers shown in Table 6.
These samples were exposed and then processed according to
Processing C or D. The results obtained are shown in Table 6.
TABLE 6
__________________________________________________________________________
Layer Addition Sample Compound where (D) Amount of (D) Gradation
(D.sub.2 -D.sub.0)/2 No. No. (D) was added (mmole/m.sup.2)
Processing Yellow Magenta Cyan Remarks
__________________________________________________________________________
4-1 101 None -- -- C 1.12 1.14 0.78 Comparison 4-2 110 (5) 11th
layer 1.0 C 1.35 1.22 0.85 Comparison 4-3 111 (21) 10th layer 1.0 C
1.29 1.25 0.87 Comparison 4-4 112 (5) 2nd and 1.0* C 1.24 1.25 1.26
Invention 3rd layers 4-5 113 (21) 2nd layer 1.0 C 1.23 1.23 1.25
Invention 4-6 101 none -- -- D 0 0 0 Comparison 4-7 110 (5) 11th
layer 1.5 D 0.42 0.30 0.22 Comparison 4-8 111 (21) 10th layer 1.5 D
0.38 0.35 0.23 Comparison 4-9 112 (5) 2nd and 1.5* D 0.39 0.40 0.41
Invention 3rd layers 4-10 113 (21) 2nd layer 1.5 D 0.37 0.38 0.40
Invention
__________________________________________________________________________
*The compound (D) was added every a half to 2nd and 3rd layers.
As is clear from Table 6, 4-4, 4-5, 4-9 and 4-10 of the Invention
showed good color balance in three colors of yellow, magenta and
cyan as compared with 4-1 to 4-3 and 4-6 to 4-8 for comparison. On
comparison with the results in Example 2, the desired density was
obtained more easily in the case where the compound of formula (D)
was in the form of a solid dispersion than in the case of an oil
dispersion thereof.
The processing methods used in the examples of the present
invention are described below. (Processing A)
After exposure, the color photographic material was processed
according to the following method (until the cumulative
replenishing amount of the solution reached three times the tank
volume) using a negative processor FP-350 manufactured by Fuji
Photo Film Co., Ltd.
______________________________________ (Processing Step) Processing
Processing Temperature Amount Step Time (.degree.C.) (ml)
______________________________________ Color 3 min. 30 sec. 40 45
development Bleaching 1 min. 00 sec. 38 20 The overflow of
bleaching solution wholly flowed into the bleach-fixing tank.
Bleach-fixing 3 min. 15 sec. 38 30 Water washing 40 sec. 35
countercurrent (1) piping system from (2) to (1) Water washing 1
min. 00 sec. 35 30 (2) Stabilization 40 sec. 38 20 Drying 1 min. 15
sec. 55 ______________________________________ * Replenishing
amount was per 35 mm (width) .times. 1.1 m (length) (corresponding
to 1 role of 24 Ex.).
The composition of each processing solution is described below.
Color Developer
______________________________________ Tank Solution Replenisher
(g) (g) ______________________________________
Diethylenetriaminepentaacetic 1.0 1.1 acid 1-Hydroxyethylidene-1,1-
2.0 2.0 diphosphonic acid Sodium sulfite 4.0 4.4 Potassium
carbonate 30.0 37.0 Potassium bromide 1.4 3.3 Potassium iodide 1.5
mg -- Hydroxylamine sulfate 2.4 2.8 4-[N-Ethyl-N-(.beta.-hydroxy-
4.5 5.5 ethyl)amino]-2-methylaniline (P-5) sulfate Water to make
1.0 l 1.0 l pH (adjusted by potassium 10.05 10.10 hydroxide and
sulfuric acid) ______________________________________
Bleaching Solution
The tank solution and the replenisher were
______________________________________ Ammonium
ethylenediaminetetraacetato 120.0 ferrate dihydrate Disodium
ethylenediaminetetraacetate 10.0 Ammonium bromide 100.0 Ammonium
nitrate 10.0 Bleaching accelerator 0.005 (CH.sub.3).sub.2
N--CH.sub.2 --CH.sub.2 --S--S--CH.sub.2 --CH.sub.2
--N(CH.sub.3).sub.2.2HCl mole Aqueous ammonia (27%) 15.0 ml Water
to make 1.0 l pH (adjusted by aqueous ammonia and 6.3 nitric acid.)
______________________________________
Bleach-fixing Solution
______________________________________ Tank Solution Replenisher
(g) (g) ______________________________________ Ammonium
ethylenediamine- 50.0 -- tetraacetato ferrate dihydrate Disodium
ethylenediamine- 5.0 2.0 tetraacetate Sodium sulfite 12.0 20.0
Aqueous solution of ammonium 240.0 ml 400.0 ml thiosulfate (700
g/liter) Aqueous ammonia (27%) 6.0 ml -- Water to make 1.0 l 1.0 l
pH (adjusted by aqueous 7.2 7.3 ammonia and acetic acid)
______________________________________
Washing Water
The tank solution and the replenisher were common.
Tap water was passed through a mixed bed column filled with an
H-type strongly acidic cation exchange resin (Amberlite IR-120B,
produced by Rhom & Haas) and an OH-type anion exchange resin
(Amberlite IR-400, produced by the same company) to reduce the
calcium and magnesium ion concentration to 3 mg/liter or less and
then thereto 20 mg/liter of dichlorinated sodium isocyanurate and
0.15 g/liter of sodium sulfate were added. The resulting solution
had a pH of from 6.5 to 7.5.
Stabilizing Solution
The tank solution and the replenisher were common.
______________________________________ (unit: g)
______________________________________ Sodium p-toluenesulfinate
0.03 Polyoxyethylene-p-monononylphenyl 0.2 ether (average
polymerization degree: 10) Disodium ethylenediaminetetraacetate
0.05 1,2,4-Triazole 1.3 1,4-Bis(1,2,4-triazole-1-ylmethyl)- 0.75
piperazine Water to make 1.0 l pH 8.5
______________________________________
Processing A is the processing method using the thus obtained
running processing solution.
(Processing B)
Processing B is the processing method using the running processing
solution obtained in the same manner as in Processing A except for
excluding Color Developing Agent P-5 sulfate in the color developer
used in Processing A.
______________________________________ (Processing C) Process-
Processing Replenishing Tank ing Time Temperature Amount Volume
Step (sec.) (.degree.C.) (ml/m.sup.2) (l)
______________________________________ Color development 60 45.0
140 2.0 Bleach-fixing 60 45.0 120 2.0 Washing (1) 15 45.0 -- 0.5
Washing (2) 15 45.0 -- 0.5 Washing (3) 15 45.0 120 0.5
Stabilization 2 room temp. coating Drying 20 85.0
______________________________________
The crossover time between the color development and the
bleach-fixing and between the bleach-fixing and the washing (1)
each was 5 seconds.
The amount of the processing solution carried over per m.sup.2 of
the photographic material was 40 ml on average.
Washing (1) to washing (3) were in a countercurrent multistage
cascade system.
Washing (1) to washing (3) were conducted in a multi-chamber water
washing system where the photographic material could transfer in
the solution by a wiper blade without making crossover in air.
Each tank was compensated for the evaporation as in JP-A-3-280042
where the external temperature and humidity of the processor was
detected by a thermohygrometer and the evaporated amount was
calculated therefrom. The water used to compensate for the
evaporation was the ion exchange water for the above-described
washing water.
The composition of the processing solution used in each step is
described below.
Color Developer
______________________________________ Mother Solution Replenisher
(g) (g) ______________________________________
Diethylenetriaminepenta- 4.0 4.0 acetic acid
1-Hydroxyethylidene-1,1- 3.0 3.0 diphosphonic acid Potassium
hydroxide 10.0 15.0 Potassium iodide 1.3 mg 0 Potassium bromide 4.0
0 Potassium carbonate 50.0 50.0 Sodium sulfite 4.0 6.8
Hydroxylamine sulfate 50.0 mmole 80.0 mmole
4-(N-Ethyl-N-.beta.-hydroxy- 40.0 mmole 55.0 mmole
ethylamino)-2-methyl- aniline (P-5) sulfate Water to make 1,000 ml
1,000 ml pH 10.10 11.80 ______________________________________
Bleach-fixinq Solution
______________________________________ Mother Solution Replenisher
______________________________________ Bleaching agent 0.15 mole
0.20 mole (ferric ammonium salt of Compound A) Ammonium ethylenedi-
0.05 mole 0.07 mole aminetetraacetato ferrate dihydrate Sulfinic
acid 0.1 mole 0.15 mole (Compound B) Fixing accelerator 0.3 mole
0.4 mole (Compound C) Ammonium thiosulfate 300 ml 400 ml (75%)
Ammonium sulfite 30 g 45 g Succinic acid 30 g 40 g Water to make
1,000 ml 1,000 ml pH 5.00 4.60
______________________________________
Washing Water
Tap water was passed through a mixed bed column filled with an
H-type strongly acidic cation exchange resin (Amberlite IR-120B,
produced by Rhom & Haas) and an OH-type strongly basic anion
exchange resin (Amberlite IR-400, produced by the same company) to
reduce the calcium and magnesium ion concentration to 3 mg/liter or
less and then thereto 20 mg/liter of dichlorinated sodium
isocyanurate and 150 mg/liter of sodium sulfate were added. The
resulting solution had a pH of from 6.5 to 7.5.
Stabilizing Solution
The mother solution and the replenisher were common.
______________________________________ Sodium p-toluenesulfinate
0.03 g Polyoxyethylene-p-monononylphenyl 0.2 g ether (average
polymerization degree: 10) Disodium ethylenediaminetetraacetate
0.05 g Water to make 1,000 ml pH 8.0
______________________________________
The bleach-fixing solution was subjected to silver recovery on the
in-line by an apparatus for recovering silver. The silver
recovering apparatus was a compact electrolytic silver recovery
apparatus using carbon as the anode and a stainless steel drum as
the cathode and the current density was 0.5 A/dm.sup.2.
The chemical formula of compounds used in the processing steps are
shown below. ##STR7##
Each sample was imagewise exposed and subjected to a continuous
processing through the above-described processing steps until the
replenishing amount of the bleach-fixing solution reached three
times the tank volume.
Processing C is the processing method using the thus obtained
running processing solution.
(Processing D)
Processing D is the processing method using the running processing
solution obtained in the same manner as in Processing C except for
excluding Color Developing Agent P-5 sulfate in the color developer
used in Processing C.
(Processing E)
After exposure, each sample was processed according to the
following method (until the cumulative replenishing amount of the
solution reached three times the mother tank volume).
______________________________________ (Processing Step) Processing
Replenishing Tank Process- Temperature Amount* Volume Step ing Time
(.degree.C.) (ml) (l) ______________________________________ Color
development 1 min. 45.0 200 2.0 30 sec. Bleaching 30 sec. 45.0 130
0.7 Fixing (1) 30 sec. 45.0 100 0.7 Fixing (2) 30 sec. 45.0 70 0.7
Washing (1) 15 sec. 45.0 -- 0.4 Washing (2) 15 sec. 45.0 -- 0.4
Washing (3) 15 sec. 45.0 400 0.4 Drying 20 sec. 80
______________________________________ *The replenishing amount was
per m.sup.2 of the photographic material. (From washing (3) to
fixing (2), a fourtank countercurrent multistage cascade system was
used.) (From fixing (2) to fixing (1), a twotank countercurrent
multistage cascade system was used.)
The composition of each processing solution is described below.
Color Developer
______________________________________ Tank Solution Replenisher
(g) (g) ______________________________________
Diethylenediaminetetra- 4.0 4.0 acetic acid Sodium 4,5-dihydroxy-
0.5 0.5 benzene-1,3-disulfonate Sodium sulfite 3.9 6.5 Potassium
carbonate 37.5 39.0 Potassium bromide 2.7 -- Potassium iodide 1.3
mg -- N-Methylhydroxylamine 4.5 5.5 sulfate
2-Methyl-4-[N-Ethyl-N-(.beta.- 8.0 12.0 hydroxyethyl)amino)aniline
sulfate Water to make 1.0 l 1.0 l pH (adjusted by potassium 10.05
10.25 hydroxide and sulfuric acid)
______________________________________
Bleaching Solution
______________________________________ Tank Solution Replenisher
(mole) (mole) ______________________________________ Ammonium
1,3-diamino- 0.33 0.50 propanetetraacetato ferrate monohydrate
Ferric nitrate 0.30 4.5 nonahydrate Ammonium bromide 0.80 1.20
Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Water to make 1.0 l
1.0 l pH (adjusted by aqueous 4.5 4.0 ammonia)
______________________________________
Fixing solution
The tank solution and the replenisher were common.
______________________________________ (g)
______________________________________ Ammonium sulfite 28 Aqueous
solution of ammonium 280 ml thiosulfate (700 g/liter) Imidazole 15
Ethylenediaminetetraacetic acid 15 Water to make 1.0 l pH (adjusted
by aqueous ammonia and 5.8 acetic acid)
______________________________________
Washing Water
The tank solution and the replenisher were common.
Tap water was passed through a mixed bed column filled with an
H-type strongly acidic cation exchange resin (Amberlite IR-120B,
produced by Rhom & Haas) and an OH-type anion exchange resin
(Amberlite IR-400, produced by the same company) to reduce the
calcium and magnesium ion concentration to 3 mg/liter or less and
then thereto 20 mg/liter of dichlorinated sodium isocyanurate and
0.15 g/liter of sodium sulfate were added. The resulting solution
had a pH of from 6.5 to 7.5.
Stabilizing Solution
The tank solution and the replenisher were common.
______________________________________ 1,2-Benzoisothiazoline-3-one
0.1 Polyoxyethylene-p-monononylphenyl 0.2 ether (average
polymerization degree: 10) Water to make 1.0 l pH (adjusted by
aqueous ammonia and 8.5 hydrochloric acid)
______________________________________
Processing E is the processing method using the thus obtained
running processing solution.
(Processing F)
Processing F is the processing method using the running processing
solution obtained in the same manner as in Processing E except for
excluding Color Developing Agent P-5 sulfate in the color developer
used in Processing E.
While the invention has been described in detail and with reference
to specific embodiments thereof, it will be apparent to one skilled
in the art that various changes and modifications can be made
therein without departing from the spirit and scope thereof.
* * * * *